Trapping of two mononuclear silyl platinum(<scp>ii</scp>)/palladium(<scp>ii</scp>) complexes and a unique dinuclear bis(μ<sub>2</sub>-disilene)(silyl)nickel(<scp>ii</scp>) complex
作者:Hao Song、Sen-Yu Zhang、Peng-Fei Gu、Hua-Yu Wu、Zi-Kun Wang、Shi Wang、Zheng Wang、Yu-Yang Gu、Yong-Hua Li
DOI:10.1039/d0nj04079g
日期:——
succeed in trapping and characterizing two mononuclear platinum and palladium silyl intermediates 4 and 5 by changing the steric hindrance of the substituents and/or ultilizing the intermediate's unique chemical reactivity, and a very unique nickel(II) 6 unprecedently, which is the first structurally characterized dinuclear silyl nickel(II) complex with a bridging μ2-disilene unit.
A Pt<sup>III</sup><sub>2</sub>Si<sub>2</sub> Four-Membered Cycle and a Dinuclear Platinum Complex Bridged by a Cyclodisiloxane Ring
作者:Shigeru Shimada、Yong-Hua Li、Maddali L. N. Rao、Masato Tanaka
DOI:10.1021/om0604019
日期:2006.7.1
Thermolysis of an equilibrium mixture of 1,2-C6H4(SiMe2)(SiH2)}Pt(dmpe) (3; dmpe = 1,2-bis(dimethylphosphino)ethane) and its dimer 4 afforded a novel dinuclear complex consisting of a Pt2Si2 four-membered cycle with formal PtIII centers as well as a small amount of an unexpected dinuclear PtII complex bridged by a cyclodisiloxane ring.
1,2-C 6 H 4(SiMe 2)(SiH 2)} Pt(dmpe)(3 ; dmpe = 1,2-双(二甲基膦基)乙烷)及其二聚体4的平衡混合物的热解提供了一种新的双核络合物,由具有正式Pt III中心的Pt 2 Si 2四元环以及少量由环二硅氧烷环桥接的意外的双核Pt II复合物组成。
Reaction of 1-(Dimethylsilyl)-2-silylbenzene with Platinum(0) Phosphine Complexes
作者:Shigeru Shimada、Maddali L. N. Rao、Yong-Hua Li、Masato Tanaka
DOI:10.1021/om050498j
日期:2005.11.1
Reaction of 1,2-C6H4(SiMe2H)(SiH3) (8) with Pt(dmpe)(PEt3)(2) (dmpe = Me2PCH2CH2PMe2) or Pt(dmpe)(2) in 1:1 ratio at room temperature gave 1,2-C6H4(SiMe2)(SiH2)}Pt-II(dmpe) (11a) as a major product in solution. Complex 11a can easily dimerize to form [(dmpe)Pt-IV(H)- 1,2-C6H4(SiMe2)(mu-SiH}](2) (12a), and 11a and 12a are in equilibrium in solution. Although monomer 11a is a major species in solution, only dimer 12a crystallized out from toluene, THF, or DMF solution. Addition of excess dmpe to a toluene solution of 11a/12a trapped the Pt-II species as a pentacoordinated dimer [1,2-C6H4(SiMe2)(SiH2)}Pt-II(dmpe)](2)( mu-dmpe) (13). A similar reaction took place between 8 and Pt(depe)(PEt3)(2) (depe = Et2PCH2CH2PEt2) or Pt(depe)(2) to give 1,2-C6H4(SiMe2)(SiH2)Pt-II(depe) (11b) and [(depe)Pt-IV(H)1,2C(6)H(4)(SiMe2)(mu-SiH)}](2) (12b), and 11b, and 12b are in equilibrium in solution. Two equivalents of 8 reacted with Pt(dmpe)(PEt3)2 in toluene at room temperature to afford two isomeric 1,2-C6H4(SiMe2H)(SiH2)}1,2-C6H4(SiMe2)(SiH2)}(H)Pt-IV(dmpe) complexes 16 and 17 in 5:3 ratio among eight possible isomers. Heating the mixture of 16 and 17 at 100 degrees C in toluene resulted in slow intramolecular dehydrogenative cyclization to afford a mixture of isomeric 1,2-C6H4(SiMe2)(SiH2)}(2)Pt-IV(dmpe) 18 and 19. The structures of complexes 12a, 12b, 13, 17, 18, and 19 were unambiguously determined by single-crystal X-ray analysis.