Silyl and diphenylsilylene derivatives of (.eta.5-C5Me5)(PMe3)2Ru. Evidence for the base-free silylene complex [(.eta.5-C5Me5)(PMe3)2Ru:SiPh2]+
Silyl and diphenylsilylene derivatives of (.eta.5-C5Me5)(PMe3)2Ru. Evidence for the base-free silylene complex [(.eta.5-C5Me5)(PMe3)2Ru:SiPh2]+
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(η5-C5Me5)(PMe3)2Ru的甲硅烷基和二苯基亚甲硅基衍生物。
DOI：
10.1021/ja00163a030
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发表时间：
1990
影响因子：
15
通讯作者：
S. Geib
中科院分区：
文献类型：
--
作者：
D. Straus;Cheng Zhang;G. Quimbita;Steven D. Grumbine;R. Heyn;T. Tilley;A. Rheingold;S. Geib
Cp*（PMe 3）2 RuCH 2SiMe 3与适当的硅烷HSiR 3在80-100°C反应，直接得到了Cp*（PMe 3）2 RuSiR 3（SiR 3 =SiEt 3（1），SiPh 3（2），SiPh 2 Me（3），SipH 2Cl（4））。其它条件导致损失1当量的PMe 3，得到钌（IV）双（甲硅烷基）物质Cp*（PMe 3）Ru（SiR 3）2 H（SiR 3 =Si（OEt）3（5），SiPh 2Cl（6），SiMe 2 OEt（7））。亲核试剂MeMgCl和LiAlH 4分别取代4中的氯离子得到3和Cp（PMe 3）2 RuSiPh 2 H（8）. 4与Me 3SiOTf在二氯甲烷中反应，高产率地得到三氟甲磺酸酯衍生物Cp*（PMe 3）2 RuSiPh 2（OTf）（9，OTf=OSO 2CF 3）.将NaBPh 4加入9的乙腈溶液中，可以分离出亚甲硅烷基加合物[Cp*（PMe 3）2 RuSiPh 2（NCMe）] BPh 4（10），为二氯甲烷溶剂化物。用X射线单晶衍射法测定了配合物10·CH 2Cl 2、10·CH 2Cl 2和10·CH 2Cl 2的晶体结构
The silyl complexes Cp*(PMe 3 ) 2 RuSiR 3 (SiR 3 =SiEt 3 (1), SiPh 3 (2), SiPh 2 Me (3), SipH 2 Cl (4)) are obtained directly by reaction of Cp*(PMe 3 ) 2 RuCH 2 SiMe 3 with the appropriate silane HSiR 3 at 80-100°C. Other conditions lead to loss of 1 equiv of PMe 3 to afford the ruthenium(IV) bis(silyl) species Cp*(PMe 3 )Ru(SiR 3 ) 2 H (SiR 3 =Si(OEt) 3 (5), SiPh 2 Cl (6), SiMe 2 OEt (7)). The nucleophilic reagents MeMgCl and LiAlH 4 displace chloride from 4 to afford 3 and Cp(PMe 3 ) 2 RuSiPh 2 H (8), respectively. The triflate derivative Cp*(PMe 3 ) 2 RuSiPh 2 (OTf) (9, OTf=OSO 2 CF 3 ) is obtained in high yield from reaction of 4 and Me 3 SiOTf in dichloromethane. Addition of NaBPh 4 to an acetonitrile solution of 9 allows isolation of the silylene adduct [Cp*(PMe 3 ) 2 RuSiPh 2 (NCMe)] BPh 4 (10) as a dichloromethane solvate. Structures of complexe 8, 9 and 10•CH 2 Cl 2 have been determined by single-crystal X-ray diffraction