EPR Spectra of [Cr(CO)2L(-C6Me6)]+ (L = PEt3, PPh3, P(OEt)3
详细信息 查看全文
- 作者：Michael P. Castellani ; Neil G. Connelly ; Robert D. Pike ; Anne L. Rieger ; and Philip H. Rieger
- 刊名：Organometallics
- 出版年：1997
- 出版时间：September 30, 1997
- 年：1997
- 卷：16
- 期：20
- 页码：4369 - 4376
- 全文大小：296K
- 年卷期：v.16,no.20(September 30, 1997)
- ISSN：1520-6041
文摘
The preparation and characterization of[Cr(CO)2L(
-C6Me6)](L = PEt3, PPh3,P(OEt)3and P(OPh)3, are reported. One-electron oxidationaffords unstable Cr(I) cations,[Cr(CO)2L(-C6Me6)]+, EPR spectraof which are reported. Detailed analysis of the anisotropic31Phyperfine interaction indicates that, in frozenCH2Cl2/THF, the phosphine andphosphitecomplexes have 2A' and 2A'' ground states,respectively. The hyperfine anisotropy can beaccounted for by dipolar interaction of the 31P nucleuswith spin density on Cr and, in thecase of the phosphite complexes, with ~0.01 P3py spin density resulting from
pi.gif" BORDER=0 >-backbonding.Line width anomalies observed in EPR spectra of these and otherCr(I) and Mn(II) "pianostool" complexes can be understood in terms of molecular distortionsresulting from solvationin frozen solutions.
-C6Me6)](L = PEt3, PPh3,P(OEt)3and P(OPh)3, are reported. One-electron oxidationaffords unstable Cr(I) cations,[Cr(CO)2L(-C6Me6)]+, EPR spectraof which are reported. Detailed analysis of the anisotropic31Phyperfine interaction indicates that, in frozenCH2Cl2/THF, the phosphine andphosphitecomplexes have 2A' and 2A'' ground states,respectively. The hyperfine anisotropy can beaccounted for by dipolar interaction of the 31P nucleuswith spin density on Cr and, in thecase of the phosphite complexes, with ~0.01 P3py spin density resulting frompi.gif" BORDER=0 >-backbonding.Line width anomalies observed in EPR spectra of these and otherCr(I) and Mn(II) "pianostool" complexes can be understood in terms of molecular distortionsresulting from solvationin frozen solutions.