Reactivity of (C5Me5)2Sm(THF)2 with Nitriles: C-C Bond Cleavage To Form Cyanide Complexes
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- 作者：William J. Evans ; Elizabeth Montalvo ; Samuel E. Foster ; Kimberly A. Harada ; Joseph W. Ziller
- 刊名：Organometallics
- 出版年：2007
- 出版时间：May 21, 2007
- 年：2007
- 卷：26
- 期：11
- 页码：2904 - 2910
- 全文大小：145K
- 年卷期：v.26,no.11(May 21, 2007)
- ISSN：1520-6041
文摘
The divalent organosamarium complex (C5Me5)2Sm(THF)2 (1) reacts in toluene with Me3CCN to formthe insoluble trivalent cyanide complex [(C5Me5)2SmCN]n (2). The Me3CCN reaction was found to proceedthrough divalent (C5Me5)2Sm(NCCMe3)(THF)x (3). The bis(nitrile) analogue of 3, (C5Me5)2Sm(NCCMe3)2(THF) (4), is isolable from the reaction of 1 with Me3CCN in THF and has been characterized by X-raycrystallography. Both 3 and 4 transform via C-C bond cleavage to form the cyanide product 2 and(C5Me5)2Sm(N=CHCMe3)(THF) (5). Complex 5 is the product of insertion of Me3CCN into a Sm-Hbond presumably formed by 
-hydrogen elimination of a Me3C intermediate. Complexes 2 and 5 canalso be generated by the stoichiometric reaction of crystalline 4 with 1 in toluene. Complex 5 can besynthesized directly from the reaction of [(C5Me5)2Sm(
-H)]2 with Me3CCN and THF. Crystallographicdata on the related nitrile adducts [(C5Me5)2Sm(NCCMe3)(-CN)]3 (6) and [(C5Me5)2Sm(NCCMe3)]2(-O) (7) are also reported.
-hydrogen elimination of a Me3C intermediate. Complexes 2 and 5 canalso be generated by the stoichiometric reaction of crystalline 4 with 1 in toluene. Complex 5 can besynthesized directly from the reaction of [(C5Me5)2Sm(-H)]2 with Me3CCN and THF. Crystallographicdata on the related nitrile adducts [(C5Me5)2Sm(NCCMe3)(-CN)]3 (6) and [(C5Me5)2Sm(NCCMe3)]2(-O) (7) are also reported.