The hydrogenation catalysts [MH(X
2)(PMP)(PPh
3)]BPh
4 (M = Ru, X = N
2,O
2; M = Os, X = H
2,) were synthesized by treatment of MHCl(PMP)(PPh
3 with NaBPh
4 under N
2, O
2 or H
2.
Reaction of OsCl
2(PMP)(PPh
3) with PhC[is equivalent to]CLi gave OsCl(PPh
3)(2-Ph
2PCH(CPh=CH)-6-Ph
2PCH
2-C
5H
3N) which reacted with NaBF
4 and NaCO
3 under H
2 to produce OsH(PPh
3)(2-Ph
2PCH(CPh=CH)-6-Ph
2PCH
2-C
5H
3N). Protonation of OsH(PPh
3)(2-Ph
2PCH(CPh=CH)-6-Ph
2PCH
2-C
5H
3N) give [Os(H
2)(2-Ph
2PCH(CPh=CH)-6-Ph
2PCH
2-C
5H
3N)(PPh
3)]BF
4 which was hydrogenated to [OsH(H
2)(2-Ph
2PCH(CPh=CH
2)-6-Ph
2PCH
2-C
5H
3N)(PPh
3)]BF
4.
Treatment of OsHCl(PPh
3)
3 with trans-Ph
2PCH
2CH
2CH=CHCH
2CH
2PPh
2 produced OsHCl(PPh
3)(trans-Ph
2PCH
2CH
2CH=CHCH
2CH
2PPh
2) which was protonated to give [Os(H
2)Cl(PPh
3)(trans-Ph
2PCH
2CH
2CH=CHCH
2CH
2PPh
2)]BF
4. It can be hydrogenated to give [OsH
2Cl(H
2)(PPh
3)(dpph)]BF
4 (dpph = 1,6-bis(diphenylphosphino)hexane).
Insertion reaction of RuHCl(CO)(η
2-cis-Cy
2PCH
2CH=CHCH
2PCy
2)(PPh
3) in MeOH and CH
2Cl
2 give RuCl(CO)(η
3-Cy
2PCH
2CHCH
2CH
2PCy
2)(PPh
3). [RuHCl(CO)(η
2-cis-Cy
2PCH
2CH=CHCH
2PCy
2)]
2(μ
2-trans-Cy
2PCH
2CH=CHCH
2PCy
2) was produced by treating RuHCl(CO)(η
2-cis-Cy
2PCH
2CH=CHCH
2PCy
2)(PPh
3) with methanol. RuCl(CO)(η
3-Cy
2PCH
2CHCH
2CH
2PCy
2)(PPh
3) was hydrogenated to give [RuH(CO)(PCy
2CH
2CH
2CH
2CH
2PCy
2)(PPh
3)]BPh
4. OsHCl(η
3-trans-Cy
2PCH=CHCH
2CH
2PCy
2)(PPh
3) reacts with HBF
4 to give [OsH
2Cl(η
3-trans-Cy
2PCH=CHCH
2CH
2PCy
2)(PPh
3)]BF
4.
Treatment of MHCl(NBD)(PPh
3)
2 (M = Ru, Os) with AgOTf produced MH(OTf)(NBD)(PPh
3)
2 (M = Ru, Os). In benzene, MH(OTf)(NBD)(PPh
3)
2 reacted with H
2 to give NBE (M = Ru) or NBN (M = Os) and [(η
6-C
6H
6)MH(PPh
3)
2]OTf. In dichloromethane, MH(OTf)(NBD)(PPh
3)
2 reacted with H
2 and PPh
3 to give NBA and RuH(OTf)(PPh
3)
4 or OsH
3(OTf)(PPh
3)
4.
In benzene, protonation of RuHCl(NBD)(PPh
3)
2 with HOTf produced NBE and [RuCl(μ-Cl)(PPh
3)
2]
2. In dichloromethane , it gave NBE and {[Ru(μ-Cl)(PPh
3)
2]
3(μ
3-C1)
2}(OTf). Treatment of RuHI(NBD)(PPh
3)
2 and [RuH(H
2O)(NBD)(PPh
3)
2]OTf with HOTf also produced NBE. Protonation of RuHCl(NBD)(PPh
3)
2 with HOAc and PPh
3 gave NBE and RuCl(OAc)(PPh
3)
3. Protonation of RuHCl(NBD)(PPh
3)
2 with DOTf or DOAc gave NBE-endo-d
1. Solution of RuH(OAc)(NBD)(PPh
3)
2 decomposed readily to give NBE.
Reaction of MC1
2(PMP)(PPh
3) (M = Ru, Os) with dppe or depe and NaBF
4 gave [MCl(PMP)(PP)]
+ (M = Ru, Os; PP = dppe, depe). Treatment of [MCl(PMP)(PP)
+ with AgOTf produced [M(H
2O)(PMP)(PP)](OTf)
2. Treatment of [Os(H
2O)(PMP)(PP)](OTf)
2 with H
2 and P
2O
5 gave [Os(H
2)(PMP)(PP)](OTf)
2 which is catalytic active for hydrogenation of cyclohexene and dimerization of styrene. In the presence of base, [M(H
2O)(PMP)(PP)](OTf)
2 reacted with hydrogen, K
2CO
3 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.
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