[钨有机金属卡宾配合物在高外压下的拉曼光谱和红外光谱研究]

[Raman and infrared spectral studies of tungsten organometallic carbyne complex at high external pressure].

作者信息

Xu Z H, Mayr A, Butler I S

机构信息

State Key Laboratory of Rare Earth Material Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.

出版信息

Guang Pu Xue Yu Guang Pu Fen Xi. 2001 Oct;21(5):596-8.

PMID:12945305

Abstract

The Raman and infrared spectra of complex: [Cl(CO)2 (DPPE) W identical to CC6H4C identical to CC6H4NC]2 Re Cl(CO)3 (DPPE = bis (diphenylphosphino) ethane, (Ph)2PCH2CH2P(Ph)2) were measured at high external pressure (up to about 50 kbar). The pressure induced phase transition was observed near 30 kbar. The pressure dependence d nu/dp of nu (W identical to C) at the low-pressure phase is a little high (0.59 cm-1.(kbar)-1) and is very low (0.04 cm-1.(kbar)-1) at the high-pressure phase. It shows that the pi-backbonding from W to pi*--orbital of CO is strengthened at the high external pressure in fragment Cl(CO)2 (DPPE) W identical to C; The bond intensity and the force constant of W identical to C and nu (W identical to C) are decreasing; This effect compete with the normal increasing nu (W identical to C) on compression.

摘要

配合物[Cl(CO)₂(DPPE)W≡CC₆H₄C≡CC₆H₄NC]₂ReCl(CO)₃（DPPE = 双（二苯基膦基）乙烷，(Ph)₂PCH₂CH₂P(Ph)₂）的拉曼光谱和红外光谱是在高外部压力（高达约50千巴）下测量的。在30千巴附近观察到压力诱导的相变。低压相下ν（W≡C）的压力依赖性dν/dp有点高（0.59 cm⁻¹·(kbar)⁻¹），而在高压相下非常低（0.04 cm⁻¹·(kbar)⁻¹）。这表明在片段Cl(CO)₂(DPPE)W≡C中，从W到CO的π*轨道的π-反馈键在高外部压力下增强；W≡C的键强度和力常数以及ν（W≡C）在降低；这种效应与压缩时ν（W≡C）正常增加的情况相互竞争。