Wittig condensation products from nickelmeso-formyl-octaethyl-porphyrin and -aetioporphyrin I and some cyclisation reactions

摘要

1660 J.C.S. Perkin I Wittig Condensation Products from Nickel meso-Formyl-octaethyl-porphyrin and -aetioporphyrin I and Some Cyclisation Reactions By Dennis P.Arnold, Richard Gaete-Holmes, Alan W. Johnson, Andrew R. P. Smith, and Geoffrey A. Williams, School of Molecular Sciences, University of Sussex, Falmer, Brighton BN1 9QJ Various Wittig condensation products from the named meso-formylporphyrins are described, together with some transformations of the products. Vilsmeier formylation of the nickel meso-vinyl derivatives causes substitution mainly in the side-chain, and acid cyclisation of the rneso-acrylaldehyde products results in the formation of a fused benzene ring and the structure of the product is fully defined by X-ray crystallography. In the absence of nickel, mild acid cyclisations of the meso-acrylaldehydes or esters yield purpurins.IN earlier paper~,l-~ we have described some reactions of the aldehyde group of nickel meso-forniyl derivatives (la) and (2a) respectively of aetioporphyrin I and octaethylporphyrin (OEP),and these included reductions to the carbinols (lb) and (2b) and the formation of M Ete R Ea Me t E tEt a R ;+. N, dN-Et rdquo;bsol;rsquo; Me / Me Et (1) M R a; Ni CHO b; Ni CH,OH c; Ni CN d; Ni CH(0H)Ph e; Ni CH=CHCO,Me i; Ni CH=CH-CH=CHCO,Me g; Ni CH=CH-CH=CHCHO h; Ni CH=CH2 i; Ni CHSHPh j; Ni CH=CH.C6H,Mek; Ni CH=CHCH, JaMe 1; Ni CH=CHCHO rn; Ni CH=CHCH20H n; Ni CH,*CH2CHa*OH 0; H2 CH=CHCHO N, ,N-Et N/ lsquo;N 0 Et Et (2) M R a; Ni CHO b; Ni CH,OH c; Ni CN d; Ni CH2 e; Ni EH2 f; Ni CH(0H)Me g; Ni CH(0H)Ph h; Ni CH=CH, i; Ni CHSHC0,Me j; Ni CH=CHMe k; Ni CH=CHPh 1; Ni CH=CHCHO m; Ni CH=CHCH,OH n; H, CH=CH.CHO 0; H, CH=CH.CO,Me /CO,Me Pi H, CH=C lsquo;COBH 9; H, CH=C(CO,H), r; Ni CH=CHCH=CH, several derivatives including the meso-cyanoporphyrins (lc) and (2c) by dehydration of the oximes.Wittig condensations: Knoevenagel condensations, Schiff base 596formation and other reactions 798 have been described in the literature. Thus, the nickel meso-formyl-porphyrins (la) and (2a) show most of the normal reac- tions of aromatic aldehydes. However, unlike other metal complexes of simple meso-substituted porphyrins, the nickel meso-formyl derivatives give bright green solutions and their electronic spectra show broadened and split Soret bands as well as an extra band at ca.650 A. W. Johnson and D. Oldfield, J. Chem. SOC.(C),1966, 794. D. P. Arnold, A. W. Johnson, and M. Winter, J.C.S. Perkin I, 1977, 1643. D. P. Arnold, A. W. Johnson, and M. Mahendran, J.C.S. Perkin I, 1978, 366. H. Callot. BUZZ.SOC.chim. France, 1973, 3413. nm. These properties are probably a measure of dis- tortion of the porphyrin ring.6 The lH n.m.r. spectra of the meso-formylporphyrins on the other hand are un- exceptional and are in line with those of the planar porphyrins. In our previous paper,2 the reaction of the primary carbinol (2b) with sulphuric acid was described. The unexpected product was the dimer (3),presumably formed by dimerisation of the radical (2d), itself formed from the carbonium ion (2e), by electron transfer from the metal porphyrin.In an attempt to define the scope of this dimerisation, we prepared 3 the methylcarbinol (2p) and the phenylcarbinol (2g) by appropriate Grignard (and now with phenyl-lithium) reactions. Reaction of the Et Et Et Et -CH2 Et Et CH*CHO//Crsquo;H Et Et ft Et Et Et methylcarbinol (2f) with sulphuric acid gave the meso-vinyl compound (2h) as expected; on the other hand, the phenylcarbinol gave (4), by a reaction involving formation of the carbonium ion, rearrangement, and loss of proton. The present paper describes a study of reactions of various Wittig products from the nickel meso-formyl porphyrins. Previously, Callot had described the con- 5 J.-H.Fuhrhop and L. Witte, Angew. Chem. Internat. Edn., 1975, 14, 361. 6 J.-H. Fuhrhop, L. Witte, and W. S. Sheldrick, Annalen, 1976, 1537; see also A. Treibs, Ann. New York Acad. Sci., 1973,206, 97. H.-H. Inhoffen and W. Nolte, Annalen, 1969, 725, 167. 8 P. S. Clezy, C. L. Lim, and J. S. Shannon, Austral. J. Chem., 1974. 27, 1103. densation of the stabilised Wittig reagent, methoxy- carbonylmethylene(tripheny1)phosphoranewith (2a) and showed that the product (2i) could be demetallated by the action of sulphuric acid. We have prepared analo- gous compounds (le) and (2i) and have used the vinylo- gous Wittig reagent, methoxycarbonylallylidene-(triphenyl) phosphorane, in the aetioporphyrin series to give (If)which was demetallated by acid treatment, and reduced to the corresponding aldehyde (lg) by treatment with a limited amount of aluminium hydride.Most of the Wittig reagents used however were prepared in situ using a mixture of the appropriate phosphonium salt and phenyl-lithium, and in this manner a range of meso-vinyl derivatives of nickel porphyrins have been prepared, comprising the meso-vinyl (lh) and (2h), -propenyl (Zj), -styryl (li) and (2k), and 9-methylstyryl(1 j) substituents. However, when (la) was treated with the bisphos-+ phonium salt, (Ph,P*CH,), 2Br-, prepared from ethylene dibromide and triphenylphosphine, in the presence of n- butyl-lithium in an attempt to prepare a bis-porphyrin, the product was, unexpectedly, the meso-heptenyl derivative (lk), presumably formed by the following mechanism : - c - cH=CH*CH2rsquo;PPh3bsol;3rdquo;- RCHI--CHCH214Me (la1 Reaction of (la) with allyl(tripheny1)phosphonium bromide in the presence of phenyl-lithium gave only the phenylcarbinol (Id).Some reactions of the nickel meso-vinylporphyrins have been carried out. Thus, although reaction of nickel meso-styrylaetioporphyrin I (li) with the Vils- meier reagent caused further meso-substitution to yield a mixture of the 10-and 15-formyl derivatives, the nickel meso-vinyl porphyrins (lh) and (2h) under similar con- ditions gave the nickel meso-acrylaldehydes (11) and (21) in ca. 85 yield by reaction at the terminal position of the side-chain.Related reactions of porphyrin @-vinyl groups have been reported by Nich01.~ Like the nickel meso-formylporphyrins (la) and (2a), the meso-acryl- aldehydes were green and showed split Soret bands. In the formylation reaction two additional green products were isolated which were shown to have been formed by meso-as well as side-chain formylation. They were dis- tinguished by the signals of the two remaining por- phyrin meso-hydrogens. The more abundant and less polar isomer showed two separate signals and was there- fore the 10-formyl derivative (5); the more polar isomer showed a single signal for the meso-hydrogens and this was the 15-formyl derivative. Reduction of the nickel meso-acrylaldehydes (11) and (21) with sodium borohydride gave the corresponding carbinols (lm) and (2m).A mixture of the aldehyde (ll), the carbinol (lm) as well as the saturated carbinol (In) was obtained by borohydride A. W. Nichol, J. Chem. SOC.(C), 1970, 903. lo R. B. Woodward, Angew. Chem., 1960, 72, 651. reduction of the meso-acrylic ester (le), but the Vils- meier route was preferable preparatively. With the meso-acrylic esters, aldehydes, and alcohols available, we have been able to extend our earlier studies on the effect of acids on porphyrins containing a variety of meso- substituents. When the met al-f ree meso-acr ylaldeh yde (en) was heated under reflux in acetic acid under nitrogen it gave an isomeric compound, the n.m.r. and electronic spectra (A,,, 440, 505, 554, 592, 672, and 734 nm) of which suggested the purpurinaldehyde structure (6a).Under these cyclisation conditions, the nickel complex (21) was unaffected. A similar cyclisation of the metal- free porphyrin containing a meso-acrylic methyl ester (20) to the purpurin (6b) was also achieved. The formation of these purpurins recalls Woodwardrsquo;s classical chloro- phyll synthesis,l* in which an unsymmetrical porphyrin was reduced in ring D to give the corresponding chlorin. That reaction was achieved using a porphyrin containing a meso-acrylic ester grouping which, first, was cyclised by heating in acetic acid to give the purpurin and then subjected to further manipulations (oxidation, hydrolysis) in order to produce the required C-17 hydrogen sub- stituent.The cyclisation, doubtless aided by steric crowding and the electron-attracting powers of the ester group, remained a unique observation until recently when Fuhrhop reported that the porphyrin meso-unsaturated dicarboxylic acid monomethyl ester (2p) was cyclised by heating in toluene to give the purpurin (6b) whereas the diacid (2q) was cyclised by treatment with concentrated sulphuric acid to give the ketone (8). When the meso-acrylaldehydes (11) and (21) were treated with concentrated sulphuric acid for 3 min at room temperature, the metal-free porphyrin aldehydes (lo) and (2n) were obtained in ca. 40 yields along with a second green product in each case. Longer exposure to sulphuric acid caused decomposition of the metal-free meso-aldehydes and after 2 h at room temperature the products were mainly (ca.40) the green products, which each possessed a fused benzene ring and a gem-dialkyl group.The same green compounds were obtained in ca. 15 yield when the nickel complexes of the 7-porphyrinylallyl alcohol (2m) were treated with sul-phuric acid in NN-dimethylformamide. The product was assigned structure (7) in the octaethylporphyrin series on the basis of its mass spectrum and n.m.r. spectra. The lH spectrum clearly demonstrated the presence of three meso-protons (6 7.72, 8.45, and 8.82), the benzenoid protons (6 7.70, 2 H and 8.8, 1 H), and the gem-diethyl group with signals at 8 0.04 (t) and 2.24 (q), recalling the lH n.m.r.spectra of the gem- dialkylporphyrin ketones of Inhoff en .rsquo;l1 The 13C spectrum assignments, fully supported by off-resonance decoupling, are shown on formula (7). The mass spectrum suggested the loss of an oxygen from the initial aldehyde (21) and the electronic spectrum of (7) showed a strong chlorin-type band at 677 nm (E 36 700) as well as a Soret band at 416 nm (E 69200). The cyclisation of the l1 H.-H. Inhoffen, J. W. Buchler, and P. Jager, Progr. Chem. Org. Nut. Prod., 1968, 26, 284. acylaldehyde side-chain to form a benzene ring formally involves a reduction step, the mechanism of which has 35.04 it7.65,119.94, 123.41 (6) a; R = CHO b; R = C02Me 88.39-, Et !e 1 not been established, although it is known that nickel porphyrin complexes can act as electron donors under acidic conditions.2 Like the nickel meso-formylporphyrins, the meso-acrylaldehyde (21) also underwent normal Wittig con- densations and a sample of the rneso-buta-l,3-dienyl derivative (2r) was prepared in good yield by this method.Crystal Structure Determination of (7).-Crystal data. C,H,,N,Ni, M 629.5. Monoclinic, a = 14.132(1), b = 16.436(1), c = 15.720(1) A, = 115.487(5)", U = 3 296.0 A3, D,= 1.268 g ~m-~,2 = 4, space group P2,/c, Mo-K, radiation (graphite crystal monochromator), A = 0.709 26 A, p = 6.24 cm-l. Crystals suitable for X-ray analysis were grown from dichloromet hane-methanol solution. Measurements were made on a crystal of approximate dimensions 0.5 x 0.2 x 0.3 mm mounted about the a-axis.Oscillation, Weissenberg, and precession photographs showed the crystals to be monoclinic, with systematic absences OkO with k odd and hOZ with Z odd uniquely determining the space group to be P2Jc. Accurate unit cell parameters, together with their estimated standard deviations (e.s.d.s) were derived by a least-squares analysis of the setting angles determined for 12 angularly well separated reflections, each with a 28 value greater than 30". All data were collected at 21 "C from a Hilger and Watts automatic four-circle diffractometer (Y290) using graphite monochromatised Mo-K, radiation (A =0.709 26 A). Intensities were measured via an W-28 scan regime within the range 28 0-50"; the intensities of 6 784 reflections were measured and 4 012 independent, statistically significant I 30(1) reflections formed the J.C.S.Perkin 1 basis for the structure determination and refinement. No significant variations in the intensities of 3 standard reflections were observed and the data were corrected for Lorentz and polarisation effects but not for absorption. The structure solution and refinement proceeded using the SHEL-X system of G. M. Sheldrick, University of Cambridge. A three-dimensional Patterson synthesis together with a Fourier and difference synthesis yielded the positions of all non-hydrogen atoms. Least-squares refinement of atomic co-ordinates and individual iso- tropic temperature factors was performed in the full- matrix mode, the function minimised being CwAF2 where w is the weight assigned to the IFo values and AF = IlFol -IFclI.After five cycles using unit weights, refinement converged with R, defined as. CAF/CJF,I, 0.0623. A further difference synthesis then yielded the positions of all hydrogen atoms and these were included TABLE1 Final atomic parameters for (7). E.s.d. values (in parentheses) refer to the least significant digits Atom la Y lb zlc Ni 0.224 4(0) -0.113 6(0) 0.939 2(0) 0.258 5(2) -0.038 2(2) 0.861 8(2) 0.364 O(2) -0.158 6(2) 0.985 4(2) N(3) 0.193 4(2) -0.184 2(2) 1.022 O(2) "4) 0.079 3(2) -0.075 7(2) 0.884 6(2) 0.355 l(3) -0.020 3(2) 0.865 l(2) 0.445 2(3) -0.064 4(2) 0.917 3(2) 0.447 8(3) -0.131 3(2) 0.968 7(2) 0.536 7(3) -0.185 5(2) 1.012 4(2) 0.638 5(3) -0.177 O(2) 1.005 4(3) 0.638 9(4) -0.221 8(3) 0.921 8(4) 0.507 l(3) -0.245 7(2) 1.054 O(2) 0.567 5(3) -0.318 7(2) 1.106 l(3) 0.533 4(4) -0.397 O(3) 1.049 l(3) 0.400 7(3) -0.227 5(2) 1.038 6(2) 0.347 6(3) -0.269 2(2) 1.081 2(2)0.254 4(3) -0.244 3(2) 1.078 2(2) 0.210 7(3) -0.281 2(2) 1.142 2(2) 0.289 l(3) -0.278 4(2) 1.246 6(3) 0.330 7f4) -0.195 O(3) 1.253 3(3) 0.177 l(3) -0.370 5(2) 1.114 6(3) 0.098 2(4) -0.382 8(3) 1.013 7(3) 0.116 7(3) -0.228 3(2) 1.118 7(2) 0.044 2(3) -0.227 4(2) 1.154 3(3) -0.039 6(3) -0.173 2(2) 1.116 l(3) -0.052 3(3) -0.126 O(2) 1.039 3(2) 0.019 O(3) -0.129 3(2) 0.998 O(2) 0.108 2(3) -0.176 8(2) 1.044 7(2) 0.000 9(3) -0.091 l(2) 0.911 O(2) -0.099 6(3) -0.068 O(2) 0.838 2(2) -0.206 5(3) -0.082 8(2) 0.832 8(2) -0.252 8(3) -0.011 3(3) 0.864 l(3) -0.080 4(3) -0.035 4(2) 0.767 5(2) -0.158 6(3) -0.006 O(3) 0.673 O(3) -0.174 7(4) -0.067 8(4) 0.596 5(3) 0.030 5(3) -0.036 9(2) 0.797 7(2) 0.082 l(3) 0.005 l(2) 0.755 7(2) 0.189 O(3) 0.009 9(2) 0.788 9(2) 0.244 l(3) 0.058 9(2) 0.749 l(2) 0.193 5(3) 0.116 2(2) 0.667 O(2) 0.157 2(4) 0.195 9(3) 0.690 O(3) 0.347 7(3) 0.041 2(2) 0.797 7(2) 0.436 8(3) 0.072 3(2) 0.779 7(2) 0.452 8(3) 0.022 5(3) 0.704 9(3) in the scattering model but were not refined, each hydrogen atom being given an isotropic temperature factor 1.5 times that of the atom to which it was bonded.All non-hydrogen atoms were then refined aniso- 1978 1663 tropically (a total of 397 variables) in two blocks and a TABLE3 weighting scheme of the form w = 1.6410/02(Fo)+ Interatomic distances (A) and angles (") in (7) 0.000 3061F,J2 was applied.Refinement converged to Intramolecular distances 0.0471. Ni-N( 1) 1.937 (3) C( 13)-C( 16) 1.546(5)R 0.0405 and R,, defined as (ZwAF2/CwlFo12)*, 1.932(3) C( 13)-C( 18) 1.495(5)The maximum shiftlerror at convergence was 0.004 and Ni-N (2) Ni-N (3) 1.930( 3) C(14)-C(15) 1.505 (6) a final difference synthesis was essentially featureless Ni-N (4) 1.953 (3) C( 16)-C (17) 1.509( 6) and showed no peaks larger than 10.4Je A-3. N(l)-C(l) 1.376( 5) C( 18)-C (19) 1.363( 7) 1.392 (4) C( 18)-C (23) 1.401(5)Final C, N, and Ni atomic parameters and their e.s.d. NP)-C(33) 1.393(5)N(2)-C(3) C(19)-C(20) 1.395 (6) values are listed in Table 1 and the H co-ordinates in N(2)-C( 10) 1.3 7 1(4) C(2O)-CI21) 1.381(6) N(3)-C(12) 1.357 (4) c(2 1)-C( 22) 1.414(6) N(3)-C(23) 1.400( 5) C(22)-C (23) 1.393 (4) TABLE2 "4)-C(24) 1.364(5) C (22)-C (24) 1.425(5) Hydrogen atom co-ordinates in (7) obtained from a N (4)-C (3 1) 1.392 (4) C (24)-C (25) 1.440 (4) difference synthesis C( 1)-C(2) 1.385(4) C( 25)-C (26) 1.495( 6) W)-C(37) 1.435(5) C(25)-C(28) 1.363(6) xla Ylb zjc C(2)-C(3) 1.355(5) C( 26)-C( 27) 1.525( 6) 0.5182 -0.0476 0.9208 C(3)-C(4) 1.450(4) C (28)-C (2 9) 1.499 (4) 0.6547 -0.1210 1.0011 C(4)-C(5) 1.495( 6) C(28)-C(31) 1.428(5) 0.6975 -0.2001 1.0633 c(4)-C (7) 1.348( 5) C(29)-C(30) 1.514( 7) 0.7176 -0.2240 0.9256 C(5)-C(6) 1.5 10 (8) C (3 1)-C ( 32) 1.364( 6) 0.5688 -0.2409 0.8595 C(7)-CW 1.496(5) C (3 2)-C (33) 1.371 (5) 0.6107 -0.2840 0.9283 C(7)-C(lO) 1.447(5) c(3 3)-C (34) 1.437 (6) 0.5539 -0.3227 1.1668 1.523 (6) c(34)-C (35) 1.506(5) 1) 1.384(6) C( 34)-C(37) 1.3 60( 5)0.6497 -0.3077 1.1218 :?I-)-(bsol; 0.5584 -0.3881 0.9989 c(11)-c(12) 1.3 6 1(6) C( 35) -C( 36) 1.507(7) 0.5720 -0.4535 1.0832 C( 12)-C( 13) 1.515 (6) C (3 7)-C (38) 1.495(6) 0.4519 -0.3993 1.0289 C(13)-C(14) 1.535 (4) C (3 8)-C (39) 1.527 (7) 0.3840 -0.3154 1.1186 0.2547 -0.3094 1.2815 Bond angles 0.3494 -0.3235 1.2544 N (2) -Ni-N ( 1) 89.5(1) C( 16)-C( 13)-C (18) 110.5( 3) 0.3626 -0.1959 1.3444 N (4) -Ni-N 1) 91.0(1) C( 16)-C( 13)-C (12) 110.9(3)0.3625 -0.1654 1.2453 N (4)-Ni-N (2) 175.1(1) C( 16)-C(13),(14) 108.8(3)0.2779 -0.1470 1.2781 N(3)-Ni-N( 1) 176.7(1) C(15)(14)-C(13) 114.8( 3) 0.1472 -0.3960 1.1550 N(3)-Ni-N(2) 90.5(1) C(17)-C( 16)-C (13) 115.0(3)0.2424 -0.4086 1.1351 N(3)-Ni-N(4) 89.3(1) C( 19)-C(18)-C(23) 121.6( 3) 0.0380 -0.3378 0.9953 C(1)-N(1)-Ni 128.6( 2) C(13)-C(18)-C(23) 107.9 (4) 0.0728 -0.4398 1.0030 C(33)-N(l)-Ni 127.1(2) C(13)-C(18)-C(19) 130.5( 3) 0.1183 -0.3653 0.9642 C(33)-N( l)-C( 1) 104.3(3) C( 20)-C( 19)-C( 18) 118.7 (4) 0.0551 -0.2564 1.2158 C(3)-N(2)-Ni 128.3 (2) C(19)-C(20)-C(21) 120.1 (5) -0.0969 -0.1606 1.1405 C( 10)-N (2)-Ni 127.0 (3) C( 20)-c (2 1)-c(22) 122.0( 3) -0.1057 -0.0821 1.0195 C( 10) -N (2)-C (3) 104.6 (3) c(23)-c ( 22)-c (24) 120.0 (4) -0.2599 -0.0991 0.7662 C( 12)-N( 3)-Ni 127.7 (3) c(21)-c(2 2)-c (24) 123.6(3) -0.1969 -0.1231 0.8729 C(12)-N (3)-C (23) 105.8(3) C( 21)-C( 22)-c(23) 116.2(3)-0.2414 0.0341 0.8330 C(23)-N( 3)-Ni 126.1 (2) C(18)(23)-N(3) 112.5(3)-0.3161 -0.0247 0.8618 C(24)-N(4)-Ni 130.1(2) C( 2 2)-C( 23)-N (3) 126.7(3) -0.2004 0.0131 0.9358 C(31)-N (4)-Ni 124.1(3) C( 18)-C( 23)-C (22) 120.7 (4) -0.1251 0.0475 0.6595 C( 3 1)-N (4)-C( 24) 105.0 (3) C (22)-C (24)-N (4) 122.7( 3) -0.2210 0.0080 0.6791 C( 2)-C( 1)-N( 1) 123.7(3) C(25)-C( 24)-N(4) 111.2( 3) -0.1 121 -0.0974 0.5916 C (3 7)-C (1 )-N( 1) 1 1 1.5(3) C(25)-C(24)-C(22) 126.0 (4) -0.2365 -0.0285 0.5443 c(3 7)-c (1)-c(2) 124.2 (4) C(26)*(25)(24) 129.0 (3) -0.2216 -0.0950 0.5434 C(1)-C(2)-C (3) 124.1( 4) C( 28)-C(25)-C( 24) 106.1(3)0.0417 0.0373 0.6962 C(2)-C(3)-N(2) 124.5( 3) C(28)-C(25)(26) 124.6(3)0.2449 0.1217 0.6328 C(4)-C(3)-N(2) 110.3(3) C (2 7)-C (26)-C (25) 114.8(3)0.1348 0.0863 0.6154 C(4)-C(3)-W 125.3 (4) C(25)-C(28)-C(31) 107.3 (3) 0.2212 0.2197 0.7318 C(5)-C(4)-C(3) 125.O (3) C(29)-C( 28)-C( 3 1) 124.8(4)0.1427 0.2305 0.6361 C(7)-C(4)-C(3) 107.1 (3) C( 29) -C (28)-C (25) 127.9 (4) 0.1092 0.1833 0.7077 C(7)-C(4)-C(5) 127.8( 3) C(30)-C(29)-C (28) 111.4( 4) 0.4235 0.1325 0.7598 C( 6)-C (514(4) 112.5(3) C (28)-C (3 1)-N (4) 110.1(3)0.4997 0.0739 0.8416 C( 8)-C (7)-C(4) 129.1(4) C( 32)-C (3 1)-N (4) 124.4( 3) 0.5111 0.0386 0.7025 c( 10)-c ( 7)-c (4) 106.6(3) C(32)-C (3 1)-C (28) 124.7(3)0.3819 0.0257 0.6429 C(10)-C( 7)-C (8) 124.3 (4) c(31)-c(3 2)-c (3 3) 125.2 (3) 0.4655 -0.0365 0.7172 c(9)-C(8)-C (7) 113.3 (3) C (32)-C (33)-N ( 1) 123.5( 3) (1 Hydrogen atoms are labelled with the carbon atom to C( 7)-C (10)-N (2) 111.4( 3) C(34)-C( 33)-N( 1) 110.8(3) which they are attached in parentheses.C(1l)-C( 10)-N(2) 124.3 (3) c(34)-c (3 3)-c (3 2) 125.6( 3) C(1l)-C( 10)-C( 7) 123.9( 3) c(35)-c (34)-c (3 3) 125.2 (3) C( 12)-C( ll)-c(10) 123.6( 3) C(37)-C(34)-C(33) 106.8 (3) Table 2. Atomic scattering curves for H, C, N, and N C( 11)-C ( 12)-N( 3) 125.1 (4) c(37)-c (34)-c (35) 127.9( 4) were taken from refs. 12 and 13, with that for Ni modi- C( 13)-C( 12)-N(3) 113.4(3) C (3 4) -C (3 5)-C (3 6) 115.0 (4) C(13)-C(12)-C( 11) 121.4( 3) C (38)-C (3 7)-C (1) 125.5( 3) fied for the real and imaginary anomalous dispersion C(12)-C(13)-C(18) 100.1(3) C(34)-C(37)-C( 1) 106.6 (3) C(14)-C(13)-C(18) 113.7 (3) C (34)-C (3 7)-C (38) 127.7 (3) l2 D.T. Cromer and J. B. Mann, Acta Cryst., 1968, A24, C(14)-C(13)-C( 12) 112.7 (3) C (3 7)-C (38)-C (3 9) 112.2( 3) 321. l3 R. F. Stewart, E. R. Davidson, and W. T. Simpson, J. Chem. corrections.14 All computations were performed on the Phys., 1965, 42, 3175. l4 D. T. Cromer and D. Liberman, J. Chem. Phys., 1970, 53, Atlas computer laboratory's ICL 1906A computer. 1891. Observed and calculated structure factors together with the thermal parameters are available as Supplementary Publication No. 22369 (15 pp.).* DISCUSSION Interatomic distances, angles, and e.s.d.s are given in Table 3, and the molecular geometry and atom number- ing are shown in Figure 1.The four Ni-N bond distances show considerable variation, from 1.930(3) to 1.953(3)A. The N(1)-Ni-N(3) and N(2)-Ni-N(4) angles are sig- nificantly different from 180" 175.1(1), 176.7(1)", and indicate a small distortion away from the normal square-planar nickel co-ordination generally observed in Anickel(11) porphyrin c~mplexes.~~-~*mean plane through the four nitrogen atoms confirms the lack of planarity within the co-ordination group (Table a), and FIGURE ORTEP drawing showing the atom numbering and 1 molecular geometry of (7) with 35 thermal ellipsoids the deviations of the nitrogen at6ms from the mean plane suggest a departure from square planarity about the nickel atom. Each of the four five-membered rings is essentially planar, as too is the benzene ring (Table 5), with the two five-membered rings nearest to the benzene ring showing the larger deviations from planarity. The bond distances and angles of rings B, c, and D in (7) and the associated porphin skeleton are similar to those usually found in metalloporphyrin complexes,ls.l9where-as in the remaining five-membered ring, the bond lengths and angles reflect the loss of conjugation. It is of interest to compare the present structure with those of the two forms of octaethylporphinatonickel(I1) (NiOPE). The tetragonal form of NiOEP l7 is largely distorted from planarity and has an Ni-N distance of 1.929(3) A which is very short for a metalloporphyrin. * For details of the Supplementary Publications Scheme see Notice to Authors No.7 in J.C.S. Petkin I, 1977, Index issue. l5 E. B. Fleischer, J. Amer. Chem. Soc., 1963, 85, 146. l6 T. A. Hamor, W. S. Caughey, and J. L. Hoard, J. Amer, Chem. Soc.. 1965. 87. 2305..~. J.C.S. Perkin I The triclinic form of NiOEP l8 is essentially planar (the angle between planes of adjacent pyrrole rings is 2.1" TABLE4 Distances (A) from the mean planes passing through (a) the four pyrrole nitrogen atoms N(1), N(2), N(3), N(4); (b) the five carbon atoms C(13), C(14), C(15), C(16), (417) (4 (b)NU) -0.068 C(13) -0.002 N(2) 0.069 C(14) -0.010 -0.069 c( 0.006 5, 0.0100.068 C(16)Ni -0.014 C117) -0.004 TABLE5 (i) Distances (A) of atoms from the mean planes passing through the five-membered rings and benzene ring, and (ii) angles between the normals to these means planes and the mean plane (6) through the co-ordination atoms N(l), N(2), N(3), N(4).(i) Deviations from mean planes (a) Plane 1: N(l), C(1), C(37), C(34), C(33) N(1) -0.011 C(1) 0.014 C(37) -0.012 C(34) 0.006 C(33) 0.003 (b) Plane 2: N(2), C(3), C(4), C(7), C(10) N(2) 0.006 C(3) 0.001 (74) -0.008 (37) 0.011 C(10) -0.010 (c) Plane 3: N(3), C(12), C(13), C(18), C(23) N(3) -0.007 C( 12) -0.014 C(13) 0.028 C(W -0.034 (723) 0.028 (d) Rane 4: N(4), C(24), C(25), C(28), C(31) N(4) 0.027 C(24) -0.018 (725) 0.001 C(28) 0.016 (731) -0.026 (e) Plane 5: C(18), C(19), C(20), C(21), C(22), C(23) 0.013::;;; 0.029 C(20) -0.031 C(21) -0.008 C(22) 0.049 C(23) -0.052 (ii) Dihedral angles Planes Angle (") Planes Angle (") 1,6 10.8 1,4 18.0 2,6 11.4 1,5 27.4 3,6 15.8 2,3 19.8 436 20.6 2,4 31.8 5,6 17.8 2,5 24.0 192 17.6 3,4 28.1 1,3 26.3 3,5 5.2 4.5 25.6 compared with an angle of 32.8"in the tetragonal form) and has an Ni-N distance of 1.958(2)A.In both forms l7 E. F. Meyer, Acta Cryst., 1972, B28,2162. l* D. L. Cullen and E. F. Meyer, J.Amer. Chem. Soc., 1974, 96, 2095. l* J. L. Hoard, Ann. N.Y. Aca,d. Sci., 1973, 206, 18. the nickel atom has square-planar co-ordination. As observed in the tetragonal form of NiOEP, and in con- trast to the essentially planar metalloporphyrin struc- tures usually observed, the present structure determin- ation of (7) shows the macrocyclic ligand to be severely non-planar.This is evident from the side-view of the molecule shown in Figure 2. The angles between normals to mean planes through the five-membered rings and benzene ring and the mean N, co-ordination plane are given in Table 5. Three of the Ni-N bond lengths in (7) 1.930(3), 1.932(3),and I .937(3)A are comparable to the relatively short Ni-N (porphyrin) distance of 1.929(3)A found in tetragonal NiOEP, and it can be postulated that the deformation of the macrocycle of (7) from planarity is necessary to decrease the Ni-N bond lengths. The normal radius of the cavity in an undistorted metallo- porphyrin has been estimated to be 2.01A,20whereas the usual Ni-N bond length found in diamagnetic nickel(I1) square-planar complexes is ca.1.85 A.21 Hence, the porphinato-core must contract from the ideal situation to accommodate a low-spin nickel@) atom. It has been postulated 19120 that 1.96 A is the smallest radius the porphyrin cavity may have in a planar structure and this is supported by experimental results; in triclinic NiOEP,18 the Ni-N distance is 1.958(2)A, in nickel@) 2,4-diacetyldeuteroporphyrin-IXdimethyl ester l6 the Ni-N distance is 1.960(8)A, in nickel(I1) aetioporphyrin I l5 the Ni-N distance is 1.957(13)A, and all three com- pounds are essentially planar. In the cases where Ni-N distances significantly less than 1.96 hi are observed, in tetragonal NiOPE and in the present study of (9),as well as in three nickel( 11) coniplexes of porphyrin-derived portant role in determining the planarlnonplanar struc- tures of the macrocyclic ligands.In tetragonal NiOEP,17 the nonplanarity is attributed to both intermolecular close contacts which would cause considerable strain in a reasonably dense planar structure and to the relief of strain caused by the small size of the nickel(i1) atom. Similarly, in the present study, the nonplanarity of the ligand in (7)is probably a result of packing forces as well as strain caused by contraction of the co-ordination group due to the relatively small nickel(I1) atom. Selec-ted intramolecular contacts, together with all significant intermolecular contact distances involving non-hydrogen atoms are given in Table 6, and each intermolecular FIGURE ORTEP drawing of (7) showing distortions of the 2 porphyrin ligand from planarity and the conformations of the terminal ethyl groups (thermal ellipsoids are drawn for 35 probability) contact is seen to involve a methylene or methyl carbon atom of a terminal ethyl group.TABLE6 N(l) -* N(3) 3.864macrocyclic ligands in 5,15-dimethyl-5,15-dihydro-N(2) -* * N(4) 3.882 octaPth3rlyorphinatonickel(IJ) 22 with average Ni-N = N(l) * -* N(2) 2.723 N(l) -* * N(4) 2.7751.908(6)A, and in two homoporphyrin nickel(I1) com- N(2) * * * N(3)plexes with average Ni-N = 1.879(4)A 23 and with Ni-N N(3) * . * N(4) 2.741 2.729 =1.886(4) k (average of three distances, fourth Ni-N (ii) Intermolecular contacts distance == 1.961(3)A) 24, the macrocyclic ligands adopt contact radii: Ni, 2.1severely nonplanar structures.C(36) * * * C(26)IHowever, nonplanar porphyriii structures are also C(9) * -C(39)'Iencountered in compounds in which there is no require- C(14) * -* NiII C(14) * * * N(1)IIment to decrease the M-N distance (where M represents C(14) * * * N(2)IIthe centre of the porphyrin cavity) from the ideal 2.01A; C(14) * --C(l)IIfor example in the tetragonal form of the free base C(14) -* -C(2)II 5,10,15,20-tetraphenylporphyrin C(14) * * * C(3)II(H2TPP)25 and in the C(16) * C(32)IIsquare-planar copper( 11) complex CuTPP 26 the copper- C(16) * * * C(33)T' (11) atom is able to occupy the porphyrin cavity with C(16) * * C(34)'I (i) Selected intramolecular -(A) within the limits of the A; C, N, 1.9 3.749 3.734 3.942 3.636 3.587 3.714 3.694 3.561 3.766 3.520 3.638 Cu-N distances very close to the optimum 2.01 A for undistorted acconimodation, as seen in the average Cu-N distance of 2.000(5)A in the essentially planar structure of copper(r1) 5,10,15,20-tetra-n-propylporphyrin271. Hence it appears that packing forces also play an im- 20 D.M. Collins and J. L. Hoard, J. A4mer. Chem. SOC.,1970, 92, 3761. 21 L. Sacconi, Transition Metal Chem., 1968, 4, 199. 22 P. N. Uwyer, J. W. Buchler, and W. R. Scheidt, J. Amer. Chem. SOC.,1974, 96, 2789. 23 B. Chevrier and R. Weiss, Inorg. Chem., 1976, 15, 770. z4 B. Chevrier and R. Weiss, J.Amer.Chem. SOC.,1975,97, 1416. a Roman numeral superscripts refer to the following co-ordinate transformations : I -x, 9 + y, 14 -2 I1 x, lamp;-y, 9 + z As seen from Figure 2,the carbon atoms of the gem-diethyl group attached to C(13) are essentially planar 25 M. J. Hamor, T. A. Hamor, and J. L. Hoard, J.Amer. Chem. SOL, 1964, 86, 1938. 26 E. B. Fleischer, C. K. Miller, and L. E. Webb, J.Amer. Chem. SOC.,1964, 86, 2342. 27 I. Moustakali and A. Tulinsky, J. Amer. Chem. SOC.,1973,95, 6811, (Table 4), the angle between the normals to this mean plane C(13), C(14), C(15), C(16), C(17) and to the mean co-ordination plane N(l), N(2), N(3), N(4) being 72.7". EXPERIMENTAL N.m.r. spectra were measured for solutions in ,HI-chloroform and u .v.-visible spectra for solutions in chloro- form (except where otherwise stated) with instruments listed in the earlier paper., Mass spectra were determined with an A.E.I.MS30 instrument by direct insertion into the ion source. Nickel meso-a-Hydroxybenzylaetiopovphyrin I ( ld).-Ally1 triphenylphosphonium chloride (55 mg) was treated with phenyl-lithium (0.042in1 of 3~ in ether) under nitrogen in tetrahydrofuran (25 ml; dried over LiAlH,). After 20 min, solid nickel wmo-fonnylaetioporphyrin I (47.5 mg) was added and the mixture stirred at room temperature for 18 h. Water (10 ml) and benzene (30 ml) were added and the organic layer separated, dried, and chromatographed on alumina using 20 chloroform-light petroleum for elution.The main band was separated, the solvent re- moved, and the residue crystallised from dichloromethane- methanol to give the product as red-violet crystals (11 mg, 20y0), m.p. 193-195 "C (Found: C, 73.2; H, 6.1; N, 9.0. C,,H,,N4Ni0 requires C, 73.0; H, 6.5; N, 8.75y0),m/e 640 (amp;I+),A 346, 408, 536, and 578 mm (E 15300, 162880, 9 130, and 15055 respectively); 6E 1.67 (m, CH, of peri- pheral Et), 3.27, 3.32, and 3.36 (all s, l : l : 2, peripheral Me), 3.45 (s, OH, exchangeable with D,O), (q, CH, of peri- pheral Et), 6.50 (m, phenyl H's), 7.69br (s, benzyl H), and 9.41 (s, 3 meso-H). meso-(P-Methoxycarbonylvivzyl)OEP (20).-The nickel complex (2i) was prepared following Callot from nickel meso-formylOEP (2a) and methoxycarbonylmethylene-(tripheny1)phosphorane.The product (2i) (100 mg) was stirred in concentrated sulphuric acid (5 ml) at room tem- perature for 2 h and then poured into ice-water and neutral- ised with sodium hydrogen carbonate. The porphyrin-free base was extracted into chloroform, the extract dried, and the solvent evaporated. The residue was chromato-graphed on alumina, using 20 hexane-chloroform for elution. The major red fraction was collected, evaporated, and the product crystallised from dichloromethane-methanol as red needles, m.p. 208-210 "C (78 mg, 85) (Found: N, 9.05. C,oH,oN,O, requires N, 9.05). Car-bon values for this compound were consistently low; A,,, 408,509,542,579, and 631 nm (E 145 000,ll 300,6 200,5 700, and 2 400 respectively); SH -3.lbr (NH), 1.66, 1.82, and 1.87 (overlapping t, CH, of peripheral Et), 3.93 (s, ester CH,), 4.0 (4,CH, of peripheral Et), 6.18 (d, J = 15 Hz, a-H of acrylic ester), 9.89 and 10.05 (both s, 1 : 2, meso-H), and 10.38 (d, J = 15 Hz, P-H of acrylic ester); vmaX.. 1 640 (C=C) and 1721 cm-l (GO).meso-( P-Methoxycavbonyvinyl) aetiopovphyrin I ( 1d) and the Nickel Complex (le).-A solution of nickel meso-formyl- aetioporphyrin I (300 mg) and methoxycarbonylmethylene-(tripheny1)phosphorane (800 mg) in xylene (24 ml) was heated under reflux for 18 h. The product was cooled and then chromatographed on silica using benzene for elution. A small fraction of nickel aetioporphyrin I was eluted first and was followed by the main band which was collected.After removal of solvent in vacuo, the residue was crystallised from dichloromethane-methanol when the prodid (Id)was obtained as small brown needles, m.p. 235-J.C.S. Perkin I 236 "C (225 mg, 68) (Found: C, 69.5; H, 6.55; N, 9.0. C36H40N4Ni02requires C, 69.8; H, 6.5; N, 9.05y0),Amx. 404, 530, and 566 nm (E 121 338, 9 415, and 13 390); vn,,,.(KBr) 1730 cm-l; 6= 1.68 (m, CH, of peripheral Et), 3.28, 3.30, and 3.35 (all s, 1 : 1 : 2, peripheral Mz), 3.80 (9, CH, of peripheral Et), 3.83 (s, ester CH,), 5.26 (d, P-H of acrylic ester, J = 15.5 Hz), 9.48 (s, 3 meso-H), and 10.20 (d, a-H of acrylic ester, J = 15.5 Hz). A solution of the nickel complex (50mg) was dissolved in concentrated sulphuric acid (3 ml) and kept for 1 h at room temperature.The solution was then poured into cold chloroform and neutralised with saturated aqueous sodium hydrogen carbonate. The chloroform layer was separated and the aqueous layer extracted with more chloroform. The combined chloroform extracts were washed and dried and the solvent removed. The residue was purified by chromatography on silica plates using 70 light petroleum- chloroform for elution. Crystallisation of the product from dichloromethane-methanol gave the product ( le) as small brown needles (24 mg, 99yo),m.p. 253-255 "C (Found: C, 76.75; H, 7.3; N, 9.95. C36H4,N40, requires C, 76.85; H, 7.5; N, 9.95),vmax.(KBr)1 730 cm-l; A 406, 506, 540, 576, and 630 nm (E 121 480, 9 860, 5 100, 4 750, and 1 580); SH -3.lbr (s, NH), 1.70 (m, CH, of peripheral Et), 3.45, 3.48, and 3.50 (all s, 1 : 1 : 2 peripheral CH,), 3.89 (4,CH, of peripheral Et), 3.93 (s, ester CH,), 6.18 (d, PH of acrylic ester, J = 15 Hz), 9.80 (s, 1 meso-H), 9.98 (s, 2 meso-H), and 10.34 (d, a-H of acrylic ester, J = 15 Hz).meso-(4-Methoxycarbonylbuta-1, 3-dienyl) aetioporphyrin and its Nickel Complex (If).-A solution of nickel meso-formylaetioporphyrin I (150 mg) and the phosphorane (384 mg) derived from tI iphenylphosphine and methyl y-bromocrotonate in xylene (12 ml) was heated under reflux for 15 h. The product was cooled and chromatographed on silica using benzene for elution. A minor fraction of nickel aetioporphyrin I was eluted first and the main fraction was then collected. After removal of the solvent in vacuo, the residue was crystallised from dichloromethane-methanol when the product (If) was obtained as small brown crystals, m.p.214deg;C(82.5mg,50~o)(Found: C, 70.25; H, 6.8; N, 8.6.C,,H,,N,NiO, requires C, 70.7; H, 6.55; N, 8.650/), 404, 533, and 563 nm (E 69 120, 6 530, and 9 220), m/e 644 (M+);vmax.(KBr)1 i20 cm-l; 6~ 1.66 (m, CH, of peripheral Et),3.20, 3.27, and 3.29 (all s, 1 : 1 : 2, peripheral CH,), 3.68 (q,CH, of peripheral Et), 3.70 (s,ester CH,, 5.51 (dd, P-H of meso-butadienyl chain, JctH+~ 14.5 Hz), 5.68 (d, 6-H of meso-butadienyl chain, J,,H~H 16 Hz), 7.80 (dd, y-H of meso-butadienyl chain, Jba-,,~11 Hz), 9.10 (d, a-H of meso-butadienyl chain, JolH+H 14.5 Hz), and 9.40 (s, 3 meso-H).The above nickel complex (45 mg! was dissolved in concentrated sulphuric acid (3 ml) and kept at room tem- perature for 1 h.The acid solution was then poured slowly onto ice and chloroform and cautiously neutralised with saturated aqueous sodium hydrogen carbonate. The chloroform layer was separated, washed, dried, and the solvent removed under reduced pressure. The residue was chromatographed on silica plates using 30 chloroform-light petroleum for elution. After removal of the solvent from the main fraction, the residue was crystallised from dichloromethane-methanol when it formed small brown needles (38 mg, 93) (Found: C, 77.2; H, 7.4; N, 9.55. C,,H4,$,02 requires C, 77.5; H, 7.55; N, 9.5), m/e 590 (M+);vmax.(KBr) 1720cm-l; SH -3.2br(s,NH), 1.72 (m,CH, of peripheral Et), 3.52, 3.55, and 3.58 (all s, 1 : 1 : 2, peri- pheral CH,), 3.82 (s, ester CH,), 3.92 (9, CH, of peripheral Et),5.93 (d, 6-H of meso-butadienyl chain, J,,H-~H = 16 Hz), 6.49 (dd, p-H of nzeso-butadienyl chain, JaH-pH 14 Hz), 8.03 (dd, y-H of meso-butadienyl chain, JsHy~ 11 Hz), 9.51 (d, a-H of meso-butadienyl chain, JaH-~~14 Hz), and 9.83 and 9.90 (both s, 1 : 2, 3 meso-H).Nickel meso-( 4-Formylbuta- 1,3-dienyZ)aetioporphyrin I (amp;).-The nickel complex (If) (50 mg) in dry tetrahydro- furan (12 ml) was treated with aluminium hydride in tetra- hydrofuran (1 ml) prepared from LiAlH, (12 mg) and AlCA, (10.3 mg) in tetrahydrofuran (2.4ml) in an atmosphere of nitrogen and the mixture stirred for 30 min. The product was treated with ether (10 ml) containing water (0.5ml) and the organic layer was separated, dried, and the solvent removed.The product was chromatographed on alumina using 30 light petroleum-chloroform for elution. The main faction was separated, the solvent removed, and the residue crystallised to give the product as dark reddish green needles, m.p. 210-211 "C (14 mg, 27) (Found: C, 71.8; H, 6.5; N, 9.05. C3,H,,AT,Si0 requires C, 72.2; H, 6.55; 1675 cm-l;N, 9.1yo),m/e 614 (M+);V,,~~.(KB~) A,,,. 400, 430, 566, and 594 nm (E 46 530, 35 790, 7 340, and 6 800 respectively). Nickel meso- Vinylaetioporphyrin I ( lh) .-Methyl- triphenylphosphonium iodide (5 10 mg) was treated with phenyl-lithium (0.4ml of 3hl-ethereal solution) in dry tetra- hydrofuran (50 ml) in an atmosphere of nitrogen.After stirring for 10 min, solid nzeso-formylacetioporphyrin I (200 mg) was added and the stirring continued for 18 h. Water (20 ml) was added followed by benzene (20 ml) and the organic layer was separated, washed, dried, and the solvent removed under reduced pressure. The residue was chroma- tographed on alumina using 20 chloroform-light petrol-eum for elution. The main fraction was separated, the solvent removed, and the residue crystallised from dichloro- methane-methanol when the product (140 mg, 70) was obtained as long dark red needles (Found: C, 72.6; H, 6.8; N, 10.0. C,,H3,N4Ni requires C, 72.75; H, 6.8; N, 10.00,/,), rn/e 560 (M+);A,,,,.404, 530, and 566 nm (E 160 110, 10 510, and 16 340 respectively), SH 1.67 (in,CH, of peripheral Et), 3.23, 3.27, and 3.30 (all s, 1 : 1 : 2, peripheral CH,), 3.78 (q, CH, of peripheral Et), 4.5 (dd, trans-p-H of vinyl), 5.78 (dd, cis-P-H of vinyl), 9.02 (dd, a-H of vinyl; Jtrans 19 Hz, Jcis 10.5 Hz, Jgcm 2 Hz), and 9.47 is, 3 nzeso-H). Nickel nieso-PropenylOEP (2j).-Ethyltriphenyl-phosphonium iodide (240 mg) was dissolved in dry tetra- stirred overnight in an atmosphere of nitrogen, the mixture was worked up in the usual manner. The residue from the organic extract after removal of solvent was chromato-graphed on alumina and eluted with 30 hexane-chloro-form. The major red fraction was separated, solvent removed, and the residue crystallised from dichloro-methane-methanol to yield the product as shining red prisms, m.p.250-252 "C (66 rng, 49) (Found: C, 76.5; H, 7.5; N, 8.25. C,,H,,N,Ni requires C, 76.2; H, 7.25; N, 8.1); A,,,. 335, 407, 532, and 568 nm (E 16 700, 154 000, 11 800, and 16 740); iSH 1.62-1.73 (overlapping t, CH, of peripheral Et), 3.77 (9, CH, of peripheral Et), 5.66 (d, J = 16.5 Hz, styryl P-H), 7.15-7.55 (m, 5 H, phenyl H), 9.35 (d, J = 16.5 Hz, styryl a-H), and 9.36 and 9.38 (both s, 1 : 2, meso-H). Nickel meso-Styrylaetioporphyrin I ( 1i) .-This compound was prepared similarly from nickel meso-formylaetio-porphyrin I (la) (80 mg) and benzyltriphenylphosphonium chloride (55 mg). The residue from the organic extract after removal of solvent was chromatographed on silica plates using 90 light petroleum-chloroform for elution.The solvent was removed and the residue crystallised from dichloromethane-methanol when the Product was obtained as red needles, m.p. 213-215 "C (53 mg, 59) (Found: C, 75.15; H, 6.55; N, 8.7. C,,H,,N,Ni requires C, 75.35; H, 6.65; N, 8.8y0),m/e 636 (M'); Amx. 405, 528, and 566 nm (E 123 290, 8 450, and 12 780); vmax. 1600 and 1500 cm-l; SH 1.68 (m, CH, of peripheral Et),3.25, 3.31, and 3.36 (all s, 1 : 1 : 2, peripheral CH,), 3.8 (q, CH, of peripheral Et), 5.68 (d, J = 15 Hz, styryl P-H), 7.42 (m, phenyl H), 9.38 (d, J = 15 Hz, styryl a-H), and 9.48 (s, 3 meso H). Nickel nieso-p-~ethg/lstyrylaetioporphyrin I ( lj).--This compound was prepared as above from (la) ( 100 mg) and p-methylbenzyl(tripheny1)phosphoniumchloride (326 mg), the product was purified by chromatography on alumina using 70 light petroleum-chloroform for elution.After removal of solvent from the main fraction, the residue was crystallised from dichloromethane-methanol when it formed small red needles, m.p. 259-260 "C (81 mg, 70) (Found: C, 75.65; H, 6.45; N, 8.6. C,,H,,N,Ni requires C, 75.6; H, 6.8; N, 8.6), Am,* 404, 530, and 564 nm (e 128 310, 9 570, and 13 645 respectively); SH 1.67 (m, CH, of peripheral Et), 2.38 (s,p-tolyl CH,), 3.25, 3.32, and 3.36 (all s, 1 : 1 : 2, peripheral CH,), 3.79 (9, CH, of peripheral Et), 5.65 (d, J =: 15.5 Hz, styryl 13-H), 7.40 (m, phenyl H), 9.38 (d, J = 15.5 Hz, styryl a-H), and 9.52 (s, 3 meso-hydrofuran (30 ml) and phenyl-lithium (0.19 ml of a 3~-solution in ether) was added under nitrogen.After the mixture had been stirred for 10 min, solid nickel nzeso-formylOEP (2a) (120 mg) was added and the stirring con- tinued overnight in an atmosphere of nitrogen; the mixture was then worked up in the usual manner. After removal of the organic solvent the residue was chromatographed on alumina using 30 hexane-chloroform for elution. The main red fraction was separated, the solvent removed, and the residue crystallised from dichloromethane-methanol to give the product as dark red needles, m.p. 275-277 "C (54 mg, 44) identical in all respects with the product prepared earlier from (2a) and triethyl phosphite. Nickel meso-StyrylOEP (214 .-Benzyl(tripheny1)-phosphonium chloride (230 mg) was dissolved in dry tetra- hydrofuran (30 ml) under nitrogen and phenyl-lithium (0.2 ml of a 3M solution in ether) was added and the mixture stirred for 10 min.Solid nickel meso-formylOEP (120 mg) was then added to the orange ylide solution and after being w. Nickel 5-(p-Forwzylvinyl)OEP (21)and 10-(5)and 15-Formyl Derivatives.-Phosphorus oxychloride (2.5 ml) was added dropwise with stirring to dry NN-dimethylformamide (1.8 ml) at 0 "C and the mixture kept at room temperature for 30 min, when a solution of nickel wzeso-vinylOEP (2 h) (180 mg) in dry dichloroethane (40 ml) was added during 5 min; the colour of the solution changed rapidly from red to green. The mixture was stirred for 10 min and then satur- ated aqueous sodium acetate (40ml) was added to it and the stirring continued for a further 15 min.The organic layer was separated, washed with water, dried, and evaporated. The residue was chromatographed on alumina using 40 hexane-chloroform and the major green fraction was collec- ted, the solvent removed, and the residue crystallised from dichloromethane-methanol to give dark green needles, m.p. 240-243 "C (150 mg, 80) (Found: C, 72.55; H, 7.1; N, 9.0. C,,H,6N,Ni0 requires C, 72.55; H, 7.2; N, 8.7), A,,,,,. 337,409, 434, 540sh, 572, and 602shnm (E 16 540, 62 200, 1668 J.C.S. Perkin I 8, respectively);7 560 and63 300, 6 390, 9 660, 1.60-1.62 sodium borohydride (5 mg) in tetrahydrofuran (25 ml) con- (overlapping t, CH, of peripheral Et), 3.50-3.69 (overlap-ping q, CH, of peripheral Et), 5.43 (dd, P-H of acrylalde- hyde), 9.30 (s, 3 meso-H), 9.63 (d, a-H of acrylaldehyde, J = 16 Hz), and 9.78 (d, formyl H, J = 8 Hz); v,,,.1 670 cm-1 (GO). Following the major green band on the chromatogram there were two other green bands which were separated and purified further by preparative t.1.c. on silica-gel plates using 30 hexane-chloroform for elution. The less polar component was separated and crystallised from dichloro- methane-methanol as shining dark green needles (10 mg, 5), m.p. 217-219 "C (Found: C, 71.55; H, 7.2; N, 8.3. C,,H,,N,NiO,requiresC, 71.35; H, 6.9;N, 8.3y0),hx.338br, 441, and 660brnm (E 15 490, 65 730, and 9 750 respectively) ; BH 1.44-1.58 (overlapping t, CH, of peripheral Et), 3.48-3.51 (overlapping q, CH, of peripheral Ei.),5.48 (dd, P-H of acrylaldehyde), 8.95 and 9.00 (both s, 2 meso-H), 9.45 (d, a-H of acrylaldehyde, J = 16 Hz), 9.78 (d, formyl-H, J = 8 Hz), and 11.60 (s, 15-formyl H).The more polar component was purified similarly and was also obtained as dark green needles (3 mg, 15) which had SH 1.52, 1.60 (t, CH, of peripheral Et), 3.52-3.56 (overlapping q, CH, of peripheral Et), 5.51 (dd, P-H of acrylaldehyde), 8.96 (s, 2 meso-H), 9.42 (d, a-H of acrylaldehyde, J = 16 Hz), 9.74 (d, formyl H, J = 8 Hz), and 11.61 (s, 10-formyl H).meso- (P-FormyZvinyl)OEP (2n).-The foregoing nickel complex (47 mg) was stirred for 3 min in concentrated sul- phuric acid (3 ml), poured onto ice, neutralised with sodium hydrogen carbonate, and extracted with chloroform.The extract was chromatographed on alumina using more chloro- form for elution when the cyclised product (7) was obtained as an initial green band followed by the demetallated product as a brown band. The latter was separated and the Product isolated and crystallised from dichloromethane-methanol to give greenish brown needles (16 mg, 37y0), m.p. 227-230 "C (Found: C, 78.8; H, 8.4; N, 9.75. C,,H,sN40 requires C, 79.55; H, 8.2; N, 9.5); Ama,.383infl, 410, 510, 543, 581, and 632 nm (E 61 500, 104 500, 10 500, 5 850, 6 800, and 3 950 respectively); BH -2.87br (NH), 1.61-1.81 (overlapping t, CH, of peripheral Et), 3.85, 3.93, and 3.95 (overlapping q, CH, of peripheral Et), 6.39 (dd, a-H of acrylaldehyde), 9.87 and 10.00 (both s, 1 : 2, meso-H), 10.22 (d, CHO), and 10.27 (d, (3-H of acrylaldehyde); vmx.1 687v, strong, sharp band cm-1 (CEO). Nickel meso-(p-FormylvinyZ)aetioporphyrinI (11) .-By a similar method, nickel meso-vinylaetioporphyrinI ( 180 mg) was converted into the meso-a-formylvinyl derivative. The product was purified by chromatography on alumina using taining water (0.5 ml) at room temperature. After 10 min the colour of the solution changed from green to red and after 1 h water (5 ml) was added followed by benzene (30 ml). The organic layer was separated, washed, dried, and the solvent removed. The residue was chromatographed on silica plates using 20 light petroleum-chloroform for elution.The main fraction was separated, the solvent removed, and the residue crystallised from dichloromethane- methanol to yield the product as dark red needles, n1.p. 234-235 "C (80 mg, 77) (Found: C, 69.0; H, 6.55; N, 9.15. C,,H,,N,NiO requires C, 69.2; H, 6.65; N, 9.2); m/e 646 (M') ; A,,,. 404, 530, and 567 nm (E 139 500, 9 420, and 14 500 respectively); 8~ 1.52 (s, OH, exchangeable with D,O), 1.70 and 1.78 (both t, CH, of peripheral Et), 3.45 (s, OH, exchangeable with D,O), 3.82 (9,CH, of peripheral Et), 4.45 (d, propenyl CK,!, 4.98 (d,J = 15 Hz, P-H of propenyl), 9.18 (d, J = 15 Hz, a-H of propenyl), and 9.42 (s, 3-meso-HI. Nickel meso- (3-Hydroxypropenyl) aetioporphyrin I ( lm).-Nickel meso-(P-formylviny1)aetioporphyrinI (11) (90 mg) was reduced similarly and gave the carbinol as red needles, m.p.230-231 "C (68 mg, 75) (Found: C, 70.9; H, 6.5; N, 9.55. C,5H,oN,IL'i0 requires C, 71.05; H, 6.8; N, 9.45); m/e 592 (M+); Am,. 404, 530, and 566 nm (E 141 540, 9 640, and 14 970 respectively); 8, 1.48 (s, OH), 1.66 (m, CH, of peripheral Et), 3.23, 3.32, and 3.35 (all s, 1 : 1 : 2, peripheral CH,), 3.78 (q, CH, of peripheral Et), 4.46 (d, propenyl CH,, collapses to s in presence of D,O), 4.98 (d, 9-H of propenyl; Ja~-fi~15 Hz), 8.98 (d, a-H of propenyl; JotH-BH15 Hz), and 9.49 (s, 3 meso-H). Nickel rneso-(3-Hydroxypropyl)aetioporplzyrinI (In).-Nickel meso-( P-methoxycarbonylvinyl) aetioporphyin I ( le) (75 nig) was treated with lithium aluminium hydride in dry tetrahydrofuran (20 ml) and heated under reflux for 3 h.Ether and aqueous ammonium chloride were added and the organic layer separated and dried. After removal of solvent the residue was chrotnatographed on silica plates when three fractions were obtained. Each was separated, solvent removed, and the products crystallised from chloroform- methanol. The fastest-running product was identified as nickel meso-(P-formylviny1)aetioporphyrinI (11) (5 mg) by direct comparison with an authentic specimen (above). The second product was similarly identified as nickel meso-( 3-hydroxypropy1)aetioporphyrin I (lm) (9 mg) and the final product (In) (26 mg, 36) was nickel meso-(3-hydroxy- propeny1)aetioporphyrin I, m.p.239-240 "C (Found: C, 70.4; H, 7.25; N, 9.5. C,,H,,N,NiO requires C, 70.85; H, 7.15; N, 9.45),m/e 594 (M'); A,,,. 338, 410, 538, and 574 nm (E 11 410, 136 990, 8 370, and 10 080 respectively); 20 light petroleum-chloroform for elution. After removal 8,1.22 (m, propyl P-CH,), 1.72 (CH, of peripheral Et), 2.29 of solvent from the main fraction, the residue was crystal- (t, propyl y-CH,), 3.28, 3.30, and 3.34 (all s, 1 : 1 : 2 peri-ised from dichloromethane-methanol when it formed dark pheral CH,), 3.82 (q, CH, of peripheral Et), 4.62 (t, propyl green needles, m.p. 225-226 "C (150 mg, 79) (Found: C. 71.15; H, 6.95; N, 9.75. C,,H,,N4Ni0 requires C, 71.45; H, 6.35; N, 9.5),m/e 588 (M+);ha,408, 436, 536, 560, and 592 nm (E 77 560, 87 040, 6 240, 8 660, and 5 970); vmax(KBr)1680 cm-l; 8H 1.68 (m, CH, of peripheral Et), 3.23, 3.28, and 3.32 (all s, 1 : 1 : 2, peripheral CH,), 3.74 (9, CH, of peripheral Et), 5.58 (dd, JaH-pH = 15.5 Hz, P-H of acrylaldehyde), 9.40 (s, 3 meso-H), 9.68 (d, J = 15 Hz, a-H of acrylaldehyde), and 9.92 (d, formyl H; J~H-,,H 7 Hz). Nickel meso-( 3-Hydroxypropeny2)OEP (2m).-Nickel meso-(P-formylviny1)OEP (21) (103 mg) was reduced with a-CH,), and 9.40 (3 meso-H).Nickel meso-Buta-1,3-dienyZOEP (2r).-Methyl-(tripheny1)phosphonium iodide (200 mg) was stirred in dry tetrahydrofuran (20 ml) under nitrogen and an ethereal solution of phenyl-lithium (0.2ml of 3M) was added. After the mixture had been stirred for 10 min, solid nickel meso-p- formylvinylOEP (20above) (100mg) was added with stirring when the initial green colour rapidly changed to red.The stirring was continued for a further 2 h, when the mixture was worked up as usual and the product after removal of solvent subjected to chromatography on alumina using 30 hexane-chloroform for elution. The major red fraction was 8, respectively);4.15and1.65, 1.15, 1,9.9, 1.1, ratios separated, the solvent removed, and the residue crystallised from dichloromethane-methanol when it was obtained as long red needles, m.p. 208-210 ldquo;C (75 nig, 75) (Found: C, 74.7; H, 7.45; N, 8.95. C,,H,,N,Ni requires C, 74.7; H, 7.5; N, 8.7Yb),A,,,. 338, 408, 534, and 568 nm (E 15 100, band. This was separated, the solvent removed, and the residue crystallised from dichloromethane-methanol when it formed brown microprisms (4 mg, 25), m.p.223-226 ldquo;G, which was identified as the purpurin (6a) (on spectral evidence, 440, 505, 554, 592, 672, and 734 nm (intensity 130 600, 10 390, and 14 970 respectively); 1.61-1.71 (overlapping t, CH, of peripheral Et), 3.75 (9, CH, of peri- pheral Et), 4.86-5.48 m, 2rsquo;-H + 2(4rsquo;-H)J, 6.75 (dt, 3rsquo;-H), (t,one CH, of peripheral Et), 1.62br (overlapping t, CH, of peripheral Et), 2.35br (q, 2 CH, of peripheral Et), 3.65br 8.8 (d, 1rsquo;-H), and 9.33 and 9.35 (both s, 1 : 2, 3 meso-H).Formation ofthe Nickel Complex (3). (i) From Nickel meso- P-FormyEviny1OEP.-Nickel P-formylvinylOEP (21) ( 100 mg) was stirred for 2 h in concentrated sulphuric acid (10 ml).The mixture was poured into ice-water (200 ml), neutralised with saturated aqueous sodium hydrogen carbonate, and extracted with chloroform to give a green solution. After the chloroform extract had been washed with water, it was dried and evaporated and the residue was chromatographed on alumina using 30 hexane-chloro-form for elution. The major green band was collected and the product purified further by preparative t.1.c. on silica using chloroform for elution. After removal of solvent the residue was crystaliised from dichloromethane-methanol, and the product was obtained as shining dark blue rods (40 mg, 41), m.p. 224-225 ldquo;C (Found: C, 74.35; H, 7.55; N, 9.15. C,,H,,N,Ni requires C, 74.4; H, 7.35; N, 8.97amp;); Amax.364, 416, 500, 566, 625, and 677 nm (E 8 860, 69 250, 5 020, 4 190, 0 780, and 36 730 respectively); vmaX. 1 645 cm-l; aH 0.04 (t, CH, of gem-Et, groups), 1.42, 1.45, 1.48, and 1.49 (overlappingt, CH, of peripheral Et), 2.28 (q, CH, of gem-Et, groups), 3.23, 3.31, 3.33, and 3.52 (overlapping d br q, CH, of peripheral Et),7.70br (d, 2 H of benzene ring), 7.72, 8.45, and 8.82 (s, 3 meso-H), and 8.9br (t, 1 H of ben- zene ring); m/e 628 (lOO~o), 599 (95), 584 (16), and 569 (20); 8~ 8.40 (q, CH, of gem-Et,), 16.07-21.45 (peri-pheral Et), 35.04 (t, CH, of gem-Et,), 59.12 (s, C bearing gem Et,), 88.39, 98.04, and 106.88 (all d, 3 meso-C), 112.31 (s, quaternary meso-C), 117.65, 119.94, and 123.48 (all d, C of benzene ring), 133.18 (l),135.03 (Z), 135.71 (I), 137.84 (I), 139.25 (I), 140.03 (Z), 141.53 (I), 141.92 (l),142.50 (1)rsquo; 143.14 (I), 144.35 (2), 147.94 (l),and 164.64 (1) (all s, ring CS).(ii) From Nickel rneso-(3-Hydroxypropenyl)OEP.-The nickel complex (2m) (45 mg) in NN-dimethylformamide (7 ml) containing sulphuric acid (3 drops of concentrated) was heated under reflux for 3 h. After 10 min the colour of the solution changed from red to green. The reaction mixture was poured into ice-water (100 ml) and the product extrac- ted into chloroform. The extract was separated, dried, and the solvent removed. The residue was chromato-graphed on alumina using 70 light petroleum-chloroform for elution. The major green fraction was collected, the solvent removed I and the residue crystallised from dichloro- methane-methanol to give the complex (7)as small greenish blue prisms (13 mg, 28) identical in all respects with the product of the previous experiment.Cyclasation of meso-P-FormylvinylOEP to (6a).-The aldehyde (2n) (I6 mg) was heated with acetic acid (4 ml) under reflux in a nitrogen atmosphere for 20 h. The acetic acid was distilled off and the resulting oil extracted with chloroform and the extract washed with aqueous sodium hydrogen carbonate and water and then dried and con-centrated. The product was then chromatographed on a column of alumina, using chloroform for elution, which gave a minor green band followed by a major greenish brown (overlapping q, CH, of peripheral Et), 4.15 (m, H-2), 8.83 (s, H of isocyclic ring), 9.09, 9.28, and 9.32 (all s, 3 meso-H), and 10.16 (s, CHO), m/e 588 (95) and 559 (100) (C39H4s-N,O requires M, 588).Cyclisation of meso-P-MethoxycarbonylvinylOEPto (6b).-(i) The porphyrin meso-acrylic ester (20) (74 mg) was heated under reflux in glacial acetic acid (20 ml) in an atmosphere of nitrogen for 24 h. The solvent was distilled off and the residue dissolved in dichloromethane ; the extract was washed several times with water, dried, and evaporated. The residue was chromatographed on alumina using 40 hexane-chloroform for elution and the major reddish brown band was separated. In solution, the product appeared red in bulk, but green in thin sections. After removal of solvent, the residue was crystallised from dichloromethane-methanol when it formed brown microneedles, m.p.243-245 ldquo;C (40 mg, 54) (Found: N, 8.95. Calc. for C,,H,,- N,O,: N, 9.05), Amx, 415infl, 430, 503, 573, 652, and 704infl nm (E 87 500, 142 800,5 700,6 960, 14 300, 6 600, and 41 000 respectively); 8~ -1.lObr (NH), -0.44 (t, one CH, of 1,2 Et groups), 1.65-1.79 (overlapping t, CH, of remaining Et), 2.5, 3.1 (m, CH, of 1,2 Et groups), 3.7-3.8 (overlapping q, CH, of peripheral Et), 3.98 (s, ester CH,), ca. 4.0 (m, 2-H), 8.66 (s, H of isocyclic ring), and 9.35, 9.40, and 9.42 (all s, 3 meso-H). (ii) The porphyrin meso-acrylic ester was heated under reflux for 3 days in dry toluene but there was no evidence of cyclisation and the starting product was recovered un-changed.Nickel meso-(Hept-l-enyl)aetioporPhyrin I (lk).-A suspension of 1,2-bis(tripheny1phosphonium)ethane di-bromide (91 mg) in anhydrous tetrahydrofuran (50 ml) was treated with n-butyl-lithium (0.48 ml of a 0.35~1-hexane solution) in a nitrogen atmosphere. After 10 min, solid nickel meso-formylaetioporphyrin I (100 mg) was added with vigorous stirring, which was continued for another 30 min, after which the mixture was heated under reflux for 30 min. It was cooled, benzene (100 ml) was added, and the product poured into water. The benzene layer was separ- ated, washed, dried, and the solvent removed. The residue was chromatographed on alumina using 50 chloroform-light petroleum (b.p. 60-80rdquo;) for elution. The first red fraction was collected and purified further by preparative t.1.c. on silica using 25 chloroform-light petroleum for elution. The major purple-red band was separated and the product crystallised from dichloromethane-methanol to give purple plates (41 mg, 39), m.p. 166-167rdquo; (Found: C, 74.3; H, 7.8; N, 9.15; m/e 630. C,,H,,N,Ni requires C, 74.25; H, 7.65; N, 8.9; Mrsquo; 630),A,, 406, 529, and 564 nm (E 160 895, 9 925, and 14 890); 8~ 0.85 (t,meso-7rsquo;-CH3), 1.3 (m, meso-4rsquo;-, 5rsquo;-, and 6rsquo;-CH,), 1.7 (CH, of P-Et), 2.4 (m, meso-3rsquo;-CH2), 3.28 (s, lP-CH,), 3.33 (s, lP-CH,), 3.35 (s, 2F3-CH3),3.8 (unsym. q, 4CH, of P-Et), 4.8 (dt, meso-Zrsquo;-CH; J1p2t = 16 Hz), and 8.6 (d, meso-1rsquo; H). A second band was eluted from the column with chloroform-light petroleum (1 : 1). The product was further separated by preparative t.1.c. on silica using chloroform-light petroleum (1 : 3) when 1670 J.C.S. Perkin I a green fraction proved to be uncharged aldehyde (la) and a We than the S.R.C. for support. One of us (G. A. W.) red fraction (6 mg, 6) after crystallisation from chloxo- thanks the University of Melbourne for a Travelling Scholar- form-methanol proved to be the corresponding carbinol (lb) ship. on the basis of comparison of u.v., i.r., and n.m.r. spectra. 8/560 Received, 29th March, 19781