Department of Chemistry, Gakushuin University, 1-5-1 Mejiro, Toshima-ku, Tokyo 171-8588, Japan.
Dalton Trans. 2010 Jul 28;39(28):6434-40. doi: 10.1039/c000545b. Epub 2010 Jun 7.
Zero-valence platinum complex [Pt(dppe)(eta(2)-C(2)H(4))] (1, dppe = 1,2-bis(diphenylphosphino)ethane) treated with disilanes HR(1)R(2)SiSiMe(3) (a, R(1) = R(2) = Me; b, R(1) = R(2) = Ph; c, R(1) = H, R(2) = Ph) afforded the corresponding disilanylplatinum hydrides [Pt(dppe)(H)(SiR(1)R(2)SiMe(3))] (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)(SiHR(1)R(2))(SiMe(3))] (3a,b) with a first-order rate constant of 7.2(2) x 10(-4) s(-1) at 25 degrees C for 2a and 3.86(4) x 10(-4) s(-1) at 40 degrees C for 2b, whereas 2c with R(1) = H followed by the transient generation of 3c dimerized rapidly to give the bis(mu-silylene)diplatinum complex Pt(dppe)(mu-SiHPh) (4c) in a mixture of cis/trans isomers. Heating of the toluene solution of 3b at 100 degrees C resulted in a similar dimerization to 4b. In addition, a trinuclear platinum complex [Pt(3)(dppe)(3)(mu(3)-SiPh)(2)] (5) with a trigonal bipyramidal Pt(3)Si(2) core arose from the reaction of 4c with 1 at 60 degrees 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.
零价铂配合物[Pt(dppe)(η2-C2H4)]（1，dppe=1,2-双（二苯基膦）乙烷）与二硅烷 HR(1)R(2)SiSiMe3（a，R(1)=R(2)=Me；b，R(1)=R(2)=Ph；c，R(1)=H，R(2)=Ph）反应，通过铂中心的 Si-H 键的氧化加成，得到相应的二硅基铂氢化物[Pt(dppe)(H)(SiR(1)R(2)SiMe3)]（2a-c）。2a，b 中的 1,2-硅基迁移导致形成双（硅基）铂配合物[Pt(dppe)(SiHR(1)R(2))(SiMe3)]（3a，b），在 25°C 下，2a 的一级速率常数为 7.2(2)×10(-4)s(-1)，在 40°C 下，2b 的一级速率常数为 3.86(4)×10(-4)s(-1)，而 R(1)=H 的 2c 随后迅速发生瞬态生成 3c 二聚体，得到顺/反异构体混合物中的双（μ-硅亚基）二铂配合物Pt(dppe)(μ-SiHPh)（4c）。3b 的甲苯溶液在 100°C 下加热导致类似的二聚化生成 4b。此外，在甲苯中，60°C 下，4c 与 1 反应生成具有三角双锥 Pt(3)Si(2)核的三核铂配合物[Pt(3)(dppe)(3)(μ3-SiPh)(2)]（5）。不对称二硅烷因此通过铂中心的 1,2-氢和硅基迁移，实现了各种单体和二聚体铂配合物的合成。
