The structures of (phenylato)(N-2-thiophenecarboxamido-meso-tetra-phenylporphyrinato)mercury(II) and bisphenylmercury(II) complex of 21-(4-tert-butyl-benzenesulfonamido)-5,10,15,20-tetraphenylporphyrin

摘要

The reaction of PhHgOAc with N-NHCO-2-C4H3S-Htpp (5) and N-p-HNSO2C6H4(tau)Bu-Htpp (4) gave a mercury (11) complex of (phenylato) (N-2-thiophenecarboxamido-meso-tetra phenylporphyrinato)mercury(II) 1.5 methylene chloride solvate [HgPh(N-NHCO2-C4H3S-tpp) center dot CH2Cl2 center dot 0.5C(6)H(14); 6 center dot CH2Cl2 center dot 0.5C(6)H(14)] and a bismercury complex of bisphenylmercury(II) complex of 21-(4-tertbutyl-benzenesulfonamido)-5,10,15,20-tetraphenylporphyrin, [(HgPh)2(N-p-(NSO2C6H4Bu)-Bu-iota-tpp); 7], respectively. The crystal structures of 6 center dot CH2O2 center dot 0.5C(6)H(14) and 7 were determined. The coordination sphere around Hg(1) in 6 center dot CH2O2 center dot 0.5C(6)H(14) and Hg(2) in 7 is a sitting-atop derivative with a seesaw geometry, whereas for the Hg(1) in 7, it is a linear coordination geometry. Both Hg(1) in 6 center dot CH2Cl2 center dot 0.5C(6)H(14) and Hg(2) in 7 acquire 4-coordination with four strong bonds [Hg(1)-N(1) = 2.586(3)angstrom, Hg(1)-N(2) = 2.118(3) angstrom, Hg(1)-N(3) = 2.625(3) angstrom, and Hg(1)-C(50) = 2.049(4) angstrom for 6 center dot CH2Cl2 center dot 0.5C(6)H(14); Hg(2)-N(1) = 2.566(6) angstrom, Hg(2)-N(2) = 2.155(6) angstrom, Hg(2)-N() = 2.583(6) angstrom, and Hg(2)-C(61) = 2.064(7) angstrom for 7]. The plane of the three pyrrole nitrogen atoms [i.e., N(1)-N(3)] strongly bonded to Hg(1) in 6 center dot CH2Cl2 center dot 0.5C(6)H(14) and to Hg(2) in 7 is adopted as a reference plane 3N. For the Hg2+ complex in 6 center dot CH2C12 center dot 0.5C(6)H(14),the pyrrole nitrogen bonded to the 2-thiophenecarboxamido ligand lies in a plane with a dihedral angle of 33.4 degrees with respect to the 3N plane, but for the bismercury(II) complex in 7, the corresponding dihedral angle for the pyrrole nitrogen bonded to the (NSO2C6H4Bu)-Bu-tau group is found to be 42.9 degrees. In the former complex, Hg(1)(2+) and N(5) are located on different sides at 1.47 and -1.29 angstrom from its 3N plane, and in the latter one, Hg(2)(2+) and N(5) are also located on different sides at -1.49 and 1.36 angstrom form its 3N plane. The Hg(1)... Hg(2) distance in 7 is 3.622(6) angstrom. Hence, no metallophilic Hg(II)... Hg(II) interaction may be anticipated. NOE difference spectroscopy, HMQC and HMBC were employed to unambiguous assignment for the H-1 and C-13 NMR resonances of 6 center dot CH2CL2 center dot 0.5C(6)H(14) in CD2Cl2 and 7 in CDCl3 at 20 degrees C. The Hg-199 chemical shift delta for a 0.05 M solution of 7 in CDCl3 solution is observed at -1074 ppm for Hg(2) nucleus with a coordination number of four and at -1191 ppm for Hg(1) nucleus with a coordination number of two. The former resonance is consistent with that chemical shift for a 0.01 M solution of 6 in CD2Cl2 having observed at 1108 ppm for Hg(1) nucleus with a coordination number of four. (C) 2007 Elsevier Ltd. All rights reserved.