Organometallics p. 1080 - 1088 (1989)
Update date:2022-07-31
Topics:
Davies, Julian A.
Eagle, Cassandra T.
Otis, Deborah E.
Venkataraman, Uma
Electrochemical reduction of cis-[PtCl2(PR3)2] (R = Ph, Et) in CH3CN/C6H6 containing NBu4ClO4 at a Hg pool electrode generates [Pt(PR3)2] equivalents in solution. Where R = Ph, the [Pt(PR3)2] equivalent may be trapped by O2, O2/CO2, HCl, MeI, C6H5COCl, and RC≡CR (R = Ph, COOMe) but not by the less reactive substrate PhCl. Where R = Et, the [Pt(PR3)2] equivalent reacts with the NBu4+ cation to ultimately generate trans-[PtH(Cl)(PEt3)2]. Prolonged electrolyses cause reduction of trans-[PtH(Cl)(PEt3)2] leading to hydride attack on the CH3CN solvent and ultimately forming trans-[PtH(CH2CN)(PEt3)2]. In the presence of bases such as NBu3, trans-[PtH(CH2CN)(PEt3)2] is isomerized in CH3CN solution producing trans-[PtCN(CH3)(PEt3)2]. The use of electroinactive trapping agents such as PhCl or PhCN as cosolvents for the reduction of cis-[PtCl2(PEt3)2] allows trapping of the [Pt(PEt3)2] equivalents as trans-[PtPh-(X)(PEt3)2] (X = Cl, CN).
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Doi:10.1039/b805069b
(2008)Doi:10.1021/om500028e
(2014)Doi:10.1016/0022-328X(94)87052-7
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(1994)
