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Title: Organometallic chemistry and catalytic properties of dihydrogen complexes
Authors: Lo, Shu-Tak
Issue Date: 2001
Abstract: The hydrogenation catalysts [MH(X2)(PMP)(PPh3)]BPh4 (M = Ru, X = N2,O2; M = Os, X = H2,) were synthesized by treatment of MHCl(PMP)(PPh3 with NaBPh4 under N2, O2 or H2. Reaction of OsCl2(PMP)(PPh3) with PhC[is equivalent to]CLi gave OsCl(PPh3)(2-Ph2PCH(CPh=CH)-6-Ph2PCH2-C5H3N) which reacted with NaBF4 and NaCO3 under H2 to produce OsH(PPh3)(2-Ph2PCH(CPh=CH)-6-Ph2PCH2-C5H3N). Protonation of OsH(PPh3)(2-Ph2PCH(CPh=CH)-6-Ph2PCH2-C5H3N) give [Os(H2)(2-Ph2PCH(CPh=CH)-6-Ph2PCH2-C5H3N)(PPh3)]BF4 which was hydrogenated to [OsH(H2)(2-Ph2PCH(CPh=CH2)-6-Ph2PCH2-C5H3N)(PPh3)]BF4. Treatment of OsHCl(PPh3)3 with trans-Ph2PCH2CH2CH=CHCH2CH2PPh2 produced OsHCl(PPh3)(trans-Ph2PCH2CH2CH=CHCH2CH2PPh2) which was protonated to give [Os(H2)Cl(PPh3)(trans-Ph2PCH2CH2CH=CHCH2CH2PPh2)]BF4. It can be hydrogenated to give [OsH2Cl(H2)(PPh3)(dpph)]BF4 (dpph = 1,6-bis(diphenylphosphino)hexane). Insertion reaction of RuHCl(CO)(η2-cis-Cy2PCH2CH=CHCH2PCy2)(PPh3) in MeOH and CH2Cl2 give RuCl(CO)(η3-Cy2PCH2CHCH2CH2PCy2)(PPh3). [RuHCl(CO)(η2-cis-Cy2PCH2CH=CHCH2PCy2)]2(μ2-trans-Cy2PCH2CH=CHCH2PCy2) was produced by treating RuHCl(CO)(η2-cis-Cy2PCH2CH=CHCH2PCy2)(PPh3) with methanol. RuCl(CO)(η3-Cy2PCH2CHCH2CH2PCy2)(PPh3) was hydrogenated to give [RuH(CO)(PCy2CH2CH2CH2CH2PCy2)(PPh3)]BPh4. OsHCl(η3-trans-Cy2PCH=CHCH2CH2PCy2)(PPh3) reacts with HBF4 to give [OsH2Cl(η3-trans-Cy2PCH=CHCH2CH2PCy2)(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-C6H6)MH(PPh3)2]OTf. In dichloromethane, MH(OTf)(NBD)(PPh3)2 reacted with H2 and PPh3 to give NBA and RuH(OTf)(PPh3)4 or OsH3(OTf)(PPh3)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 {[Ru(μ-Cl)(PPh3)2]3(μ3-C1)2}(OTf). Treatment of RuHI(NBD)(PPh3)2 and [RuH(H2O)(NBD)(PPh3)2]OTf with HOTf also produced NBE. Protonation of RuHCl(NBD)(PPh3)2 with HOAc and PPh3 gave NBE and RuCl(OAc)(PPh3)3. Protonation of RuHCl(NBD)(PPh3)2 with DOTf or DOAc gave NBE-endo-d1. Solution of RuH(OAc)(NBD)(PPh3)2 decomposed readily to give NBE. Reaction of MC12(PMP)(PPh3) (M = Ru, Os) with dppe or depe and NaBF4 gave [MCl(PMP)(PP)]+ (M = Ru, Os; PP = dppe, depe). Treatment of [MCl(PMP)(PP)+ with AgOTf produced [M(H2O)(PMP)(PP)](OTf)2. Treatment of [Os(H2O)(PMP)(PP)](OTf)2 with H2 and P2O5 gave [Os(H2)(PMP)(PP)](OTf)2 which is catalytic active for hydrogenation of cyclohexene and dimerization of styrene. In the presence of base, [M(H2O)(PMP)(PP)](OTf)2 reacted with hydrogen, K2CO3 and HC[is equivalent to]CPh to give [MH(PMP)(PP)](OTf), [M(OH)(PMP)(dppe)](OTf) and [Ru(C[is equivalent to]CPh)(PMP)(dppe)](OTf) respectively.
Description: Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2001
xxvii, 256 leaves : ill. ; 30 cm
HKUST Call Number: Thesis CHEM 2001 LoST
Appears in Collections:CHEM Doctoral Theses

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