Complex Formation and Rearrangement Reactions of the Phosphine Hydride Anions [OsH3(PPh3)3]- and [IrH2(PPh3)3]-

详细信息    查看全文

• 作者：Gemma Guilera ; G. Sean McGrady ; Jonathan W. Steed ; and Aled L. Jones
• 刊名：Organometallics
• 出版年：2006
• 出版时间：January 2, 2006
• 年：2006
• 卷：25
• 期：1
• 页码：122 - 127
• 全文大小：237K
• 年卷期：v.25,no.1(January 2, 2006)
• ISSN：1520-6041

文摘

[OsH₄(PPh₃)₃] (1) reacts with KH in THF in the presence of 18-crown-6 to form [K(THF)(18-crown-6)][OsH₃(PPh₃)₃] (2), characterized by NMR spectroscopy and X-ray crystallography; cation-anion contactis achieved through three Os-H···K moieties. In contrast, [IrH₃(PPh₃)₃] (6) reacts with KH and 18-crown-6 in THF with redistribution of ligands to produce the known bis-phosphine complex [K(18-crown-6)][IrH₄(PPh₃)₂] (7). This reaction has been followed by NMR spectroscopy, and [IrH₂(PPh₃)₃]^-has been identified as a likely intermediate. K[OsH₃(PPh₃)₃] (3) reacts with Buⁿ₃SnCl to form the tin-osmium complex [OsH₃(SnBuⁿ₃)(PPh₃)₃] (8), characterized by NMR spectroscopy and X-ray crystallography. The molecule contains a seven-coordinate osmium center, which can be described approximatelyas a distorted fac-[OsH₃(PPh₃)] arrangement, with the SnBuⁿ₃ moiety capping the OsH₃ face.