Applications of antimony and bismuth for cluster synthesis and heterogeneous catalysts.

摘要

The complex Re2(CO)8[mu-eta2-C(H)=C(H)Bu n](mu-H), 2.1 reacts with SbPh3 at 68°C to yield the new sigma-phenyl dirhenium complex Re2(CO) 8(SbPh3)(Ph)(mu-SbPh2), 2.4 in 72% yield. Compound 2.4 contains two rhenium atoms held together by a bridging SbPh2 ligand. One rhenium atom contains a sigma-phenyl group. The other rhenium atom contains a SbPh3 ligand.;The reaction of 2.1 with BiPh3 in heptane solvent at reflux yielded three new compounds Re2(CO) 8(mu-BiPh2)2, 3.1 (14% yield), [Re(CO)4(mu-BiPh2)]3, 3.2 (5% yield) and Re2(eta6-C6H5Ph)(CO) 7, 3.3, 4.7 mg (7% yield). Compound 3.1 contains two Re(CO)4 groups joined by two bridging BiPh2 ligands in a four-membered ring. There is no Re--Re bond in 3.1, Re···Re = 4.483(1) A. Compound 3.2 contains a six-membered Re3Bi3 ring in a twist-boat conformation. When heated to 110°C in toluene, compound 3.1 was transformed into the heterocycle 3.2 (8% yield), the known compound Re(CO)5Ph, 3.4 (25% yield) and the new compound Re2(CO)8(mu-BiPh)2, 3.5 (4% yield).;The heterocyclic rhenium-bismuth complex Re3(CO)12(mu-H) 2(mu-BiPh2), 3.9 was obtained in 62% yield from the reaction of [Bu4N][Re3(CO)12(mu-H) 2] with BiPh2Cl at room temperature. Compound 3.9 was converted to the [Bu4N] salt of the dihydrido monoanion [{HRe(CO) 4}2(mu-BiPh2)], 3.10 by reaction with [Bu4N][OH]. The anion of 3.10 contains a BiPh 2 ligand bridging two HRe(CO)4 groups. The corresponding [Bu4N] salt of the SbPh2-bridged monoanion [{HRe(CO) 4}2(mu-SbPh2)], 3.11 was obtained from the reaction of Re2(CO)8(mu-SbPh2)(mu-H), 2.10 with NaBH4 followed by precipitation with [Bu 4N]Br. The anion of 3.11 was converted back to 2.10 by treatment with H[BF4], but no characterizable product was obtained from the treatment of 3.10 with H[BF4].;Three products Re2[Pt(PBut3)](mu-SbPh 2)(CO)8(mu-H), 4.2, Re2[Pt(CO)(PBu t3)]Ph(CO)8(mu3-SbPh)(mu-H), 4.3 and Re2[Pt(PBut3)]2(CO) 8(mu4-Sb2Ph2)(mu-H)2, 4.4 were obtained from the reaction of Re2(CO)8(mu-SbPh 2)(mu-H), 2.10 with Pt(PBut3) 2. Compound 4.3 was also obtained from 4.2 by further reaction with Pt(PBut3)2. Compound 4.2 is a Pt(PBut3) adduct of 2.10 formed by the insertion of the platinum atom into one of the Re--Sb bonds of 2.10 with formation of two Pt--Re bonds. Compound 4.3 contains an open Re2Pt cluster and was also obtained in a low yield by the addition of CO to 4.2.;The reaction of [Re(CO)4(mu-SbPh2)]2, 2.16 with Pt(PBut3)2 in octane solvent at reflux (125°C) has yielded two platinum-rhenium-antimony compounds: Re2(CO)8[(mu-SbCH2CMe2)Pt(H)PBu t2]PBut3(mu-SbPh2), 5.1 and Re2(CO)8[Pt(CO)(CH2CMe 2)PBut2](mu3-SbPh)(mu-SbPh 2), 5.2 in low yields. Both products were formed by cleavage of phenyl group(s) from one of the bridging SbPh2 ligands in 2.16 and addition of a PtPBut3 or Pt[PBu t3]2 group to the antimony atom. In both products one of the t-butyl groups was metalated on one of its methyl groups.;Pt(PBut3)2 reacts with the rhenium-hydride complex HRe(CO)4(SbPh3), 2.5 at 25°C to give the complex PtRe(CO)4(Ph)(PBut3)(mu-SbPh2)(mu-H), 6.1 in 75% yield by the oxidative-addition of a PtPBut 3 group into an Sb--C bond on the SbPh3 ligand of 2.5. Compound 6.1 contains a Pt--Re bond, Pt(1)--Re(1) = 3.0971(7) A, with a bridging SbPh2 ligand and a bridging hydrido ligand. At 98°C, Pt(PBut3)2 reacts with two equivalents of 2.5 to yield the compounds PtRe2(CO) 8[PH(But2)](Ph)(mu-SbPh2) 2(mu-H), 6.2, PtRe2(CO)8(SbPh 3)(Ph)(mu-SbPh2)2(mu-H), 6.3 and PtRe2(P-t-Bu3)(mu-SbPh 2)2(mu-SbPh), 6.4. Compounds 6.2 and 6.3 both contain five-membered Re2Sb2Pt rings formed from two mutually-bonded Re(CO)4 groups and two bridging SbPh2 ligands that are both bonded to the Pt atom. (Abstract shortened by UMI.)