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• W2016124545 abstract "Reactions of the linearly ordered Pt2Pd mixed-metal complex linear-[Pt2Pd(μ-dpmp)2(XylNC)2](PF6)2 (1b) (dpmp = bis(diphenylphosphinomethyl)phenylphosphine, XylNC = 2,6-xylyl isocyanide), with electron-deficient alkynes, RC⋮CR‘, led to the formation of a series of unsymmetrical A-frame clusters formulated as [Pt2Pd(μ-dpmp)(μ-Ph2PCH2P(Ph)CH2P(Ph)2CRCR‘)(XylNC)2](PF6)2 (R = R‘ = CO2Me (2); R = R‘ = CO2Et (3); R = H, R‘ = CO2Me (4); R = H, R‘ = CO2Et (5); R = CH3, R‘ = CO2Et (6)) in considerable yields, in which the alkyne molecule was site-selectively inserted into the Pt−Pd bond and was further reacted with a phosphine unit of a dpmp ligand through double bond breaking of the C⋮C unit. Complexes 2−6 were characterized by IR, electronic absorption, and NMR spectroscopic techniques and X-ray crystallography (2, 4, and 5) to reveal that the apparent double insertion of the acetylene unit takes place site-selectively on the Pt−Pd−P heterometallic center. In complexes 4 and 5, the P−C bond formation occurred regioselectively between the terminal alkyne carbon and phosphine unit of dpmp, resulting in a μ-η1:η2-phosphorus C2 ylide bridging structure. The reaction mechanism was discussed. In contrast, reaction of 1b with excess HBF4 afforded [Pt2Pd(μ-H)(dpmp)2(XylNC)2](BF4)3 (8), where a proton was oxidatively added to the Pt−Pt bond vs the Pt−Pd bond. From the X-ray crystal structure of 8, the structural change accompanied by the addition was revealed to be fairly small, with a slight elongation of the Pt−Pt bond from 2.690(1) Å (1b) to 2.867(2) Å (8). These results demonstrated that the heterometal (Pd) was able to alter the reactivity of the linear trimetallic clusters and interestingly regulated its specificity." @default.
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• W2016124545 date "2000-12-08" @default.
• W2016124545 modified "2023-10-16" @default.
• W2016124545 title "Unsymmetrical A-Frame Pt₂Pd Trinuclear Complexes: Site-Selective Apparent Double Insertion of Alkynes into Pd−Pt and Pd−P Bonds" @default.
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• W2016124545 doi "https://doi.org/10.1021/om000747y" @default.
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