Thorium(IV) and Uranium(IV) Ketimide Complexes Prepared by Nitrile Insertion into Actinide-Alkyl and -Aryl Bonds
详细信息 查看全文
- 作者：Kimberly C. Jantunen ; Carol J. Burns ; Ingrid Castro-Rodriguez ; Ryan E. Da Re ; Jeffery T. Golden ; David E. Morris ; Brian L. Scott ; Felicia L. Taw ; and Jaqueline L. Kiplinger
- 刊名：Organometallics
- 出版年：2004
- 出版时间：September 27, 2004
- 年：2004
- 卷：23
- 期：20
- 页码：4682 - 4692
- 全文大小：247K
- 年卷期：v.23,no.20(September 27, 2004)
- ISSN：1520-6041
文摘
Migratory insertion of benzonitrile into both An-C bonds of the bis(alkyl) and bis(aryl)complexes (C5Me5)2AnR2 yields the actinide ketimido complexes (C5Me5)2An[-N=C(Ph)(R)]2(where An = Th, R = Ph, CH2Ph, CH3; An = U, R = CH2Ph, CH3) and provides a versatilemethod for the construction of electronically and sterically diverse ketimide ligands. TheTh(IV) compounds represent the first examples of thorium ketimide complexes. The uraniumcomplexes are surprisingly unreactive, and both the uranium and thorium bis(ketimido)complexes display unusual electronic structure properties. The combined chemical andphysical properties of these complexes suggest a higher An-N bond order due to significantligand-to-metal 
-bonding in the actinide ketimido interactions and indicate that thef-electrons in mid-valent organouranium complexes might be far more involved in chemicalbonding and reactivity than previously thought. We also report herein the structures of theknown thorium and uranium complexes (C5Me5)2Th(CH2Ph)2, (C5Me5)2ThMe2, (C5Me5)2U(CH2Ph)2, and (C5Me5)2UMe2.
-bonding in the actinide ketimido interactions and indicate that thef-electrons in mid-valent organouranium complexes might be far more involved in chemicalbonding and reactivity than previously thought. We also report herein the structures of theknown thorium and uranium complexes (C5Me5)2Th(CH2Ph)2, (C5Me5)2ThMe2, (C5Me5)2U(CH2Ph)2, and (C5Me5)2UMe2.