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Issue 28, 2010
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Syntheses of mono- and dinuclear silylplatinum complexes bearing a diphosphino ligand via stepwise bond activation of unsymmetric disilanes

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Abstract

Zero-valence platinum complex [Pt(dppe)(η2-C2H4)] (1, dppe = 1,2-bis(diphenylphosphino)ethane) treated with disilanes HR1R2SiSiMe3 (a, R1 = R2 = Me; b, R1 = R2 = Ph; c, R1 = H, R2 = Ph) afforded the corresponding disilanylplatinum hydrides [Pt(dppe)(H)(SiR1R2SiMe3)] (2a–c) by oxidative addition of the Si–H bond to the platinum center. The 1,2-silyl migration in 2a,b led to the formation of bis(silyl)platinum complexes [Pt(dppe)(SiHR1R2)(SiMe3)] (3a,b) with a first-order rate constant of 7.2(2) × 10−4 s−1 at 25 °C for 2a and 3.86(4) × 10−4 s−1 at 40 °C for 2b, whereas 2c with R1 = H followed by the transient generation of 3c dimerized rapidly to give the bis(μ-silylene)diplatinum complex [Pt(dppe)(μ-SiHPh)]2 (4c) in a mixture of cis/trans isomers. Heating of the toluene solution of 3b at 100 °C resulted in a similar dimerization to 4b. In addition, a trinuclear platinum complex [Pt3(dppe)33-SiPh)2] (5) with a trigonal bipyramidal Pt3Si2 core arose from the reaction of 4c with 1 at 60 °C in toluene. Unsymmetric disilanes therefore accomplished the syntheses of various monomeric and dimeric platinum complexes via 1,2-hydrogen and silyl migration to the platinum center.

Graphical abstract: Syntheses of mono- and dinuclear silylplatinum complexes bearing a diphosphino ligand via stepwise bond activation of unsymmetric disilanes

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Publication details

The article was received on 11 Jan 2010, accepted on 07 May 2010 and first published on 07 Jun 2010


Article type: Paper
DOI: 10.1039/C000545B
Citation: Dalton Trans., 2010,39, 6434-6440
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    Syntheses of mono- and dinuclear silylplatinum complexes bearing a diphosphino ligand via stepwise bond activation of unsymmetric disilanes

    H. Arii, M. Takahashi, M. Nanjo and K. Mochida, Dalton Trans., 2010, 39, 6434
    DOI: 10.1039/C000545B

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