Organometallic chemistry and catalytic properties of dihydrogen complexes.

摘要

The hydrogenation catalysts [MH(X₂)(PMP)(PPh₃)]BPh ₄ (M = Ru, X = N₂, O₂; M = Os, X = H₂,) were synthesized by treatment of MHCl(PMP)(PPh₃) with NaBPh ₄ under N₂, O₂ or H₂.; Reaction of OsCl₂(PMP)(PPh₃) with PhC≡CLi gave OsCl(PPh₃)(2-Ph₂PCH(CPh=CH)-6-Ph₂PCH ₂-C₅H₃N) which reacted with NaBF₄ and NaCO₃ under H₂ to produce OsH(PPh₃)(2-Ph ₂PCH(CPh=CH)-6-Ph₂PCH₂-C₅H₃N). Protonation of OsH(PPh₃)(2-Ph₂PCH(CPh=CH)-6-Ph ₂PCH₂-C₅H₃N) give [Os(H₂)(2-Ph ₂PCH(CPh=CH)-6-Ph₂PCH₂-C₅H₃N)(PPh ₃)]BF₄ which was hydrogenated to [OsH(H₂)(2-Ph ₂PCH(CPh=CH₂)-6-Ph₂PCH₂-C₅H ₃N)(PPh₃)]BF₄.; Treatment of OsHCl(PPh₃)₃ with trans-Ph ₂PCH₂CH₂CH=CHCH₂CH₂PPh ₂ produced OsHCl(PPh₃)(trans-Ph₂PCH ₂CH₂CH=CHCH₂CH₂PPh₂) which was protonated to give [Os(H₂)Cl(PPh₃)(trans -Ph₂PCH₂CH₂CH=CHCH₂CH ₂PPh₂)]BF₄. It can be hydrogenated to give [OsH ₂Cl(H₂)(PPh₃)(dpph)]BF₄ (dpph = 1,6-bis(diphenylphosphino)hexane).; Insertion reaction of RuHCl(CO)(η2-cis-Cy ₂PCH₂CH=CHCH₂PCy₂)(PPh₃) in MeOH and CH₂Cl₂ give RuCl(CO)(η3-Cy ₂PCH₂CHCH₂CH₂PCy₂)(PPh ₃). [RuHCl(CO)(η2-cis-Cy₂PCH ₂CH=CHCH₂PCy₂)]₂(μ₂- trans-Cy₂PCH₂CH=CHCH₂PCy₂) was produced by treating RuHCl(CO)(η2-cis-Cy ₂PCH₂CH=CHCH₂PCy₂)(PPh₃) with methanol. RuCl(CO)(η3-Cy₂PCH₂CHCH ₂CH₂PCy₂)(PPh₃) was hydrogenated to give [RuH(CO)(PCy₂CH₂CH₂CH₂CH ₂PCy₂)(PPh₃)]BPh₄. OsHCl(η 3-trans-Cy₂PCH=CHCH₂CH ₂PCy₂)(PPh₃) reacts with HBF₄ to give [OsH₂Cl(η3-trans-Cy₂PCH=CHCH ₂CH₂PCy₂)(PPh₃)]BF₄.; Treatment of MHCl(NBD)(PPh₃)₂ (M = Ru, Os) with AgOTf produced MH(OTf)(NBD)(PPh₃)₂ (M = Ru, Os). In benzene, MH(OTf)(NBD)(PPh₃)₂ reacted with H₂ to give NBE (M = Ru) or NBN (M = Os) and [(η6-C₆H ₆)MH(PPh₃)₂]OTf. In dichloromethane, MH(OTf)(NBD)(PPh ₃)₂ reacted with H₂ and PPh₃ to give NBA and RuH(OTf)(PPh₃)₄ or OsH₃(OTf)(PPh ₃)₄.; In benzene, protonation of RuHCl(NBD)(PPh₃)₂ with HOTf produced NBE and [RuCl(μ-Cl)(PPh₃)₂]₂. In dichloromethane, it gave NBE and {lcub}[Ru(μ-Cl)(PPh₃)₂] ₃