The Uncommon Reactivity of Dihapto-Coordinated Nitrile, Ketone, and Alkene Ligands When Bound to a Powerful -Base
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- 作者：Edward C. Lis ; Jr. ; David A. Delafuente ; Yunqing Lin ; Christopher J. Mocella ; Michael A. Todd ; Weijun Liu ; Michal Sabat ; William H. Myers ; W. Dean Harman
- 刊名：Organometallics
- 出版年：2006
- 出版时间：October 9, 2006
- 年：2006
- 卷：25
- 期：21
- 页码：5051 - 5058
- 全文大小：141K
- 年卷期：v.25,no.21(October 9, 2006)
- ISSN：1520-6041
文摘
A series of complexes of the form TpM(NO)(L')(
2-L) are prepared (where L is a nitrile, ketone, oralkene, M = W or Mo, L' = PMe3, MeIm, Tp = hydridotris(pyrazolyl)borate). These complexes aresubjected to various electrophiles (e.g., alkyl halides, Br
nsted acids) to systematically probe the abilityof the 
-basic transition metal to affect the reactivity of the dihapto-coordinated ligand. Alkylation isobserved at the heteroatom of the ketone and the nitrile, but depending on the reagent, alkylation of thenitrosyl ligand or addition to the complexed -bond also occurs. The structures of several nitriliumcomplexes and a rare example of an 2-acetonium complex are also reported.
2-L) are prepared (where L is a nitrile, ketone, oralkene, M = W or Mo, L' = PMe3, MeIm, Tp = hydridotris(pyrazolyl)borate). These complexes aresubjected to various electrophiles (e.g., alkyl halides, Brnsted acids) to systematically probe the abilityof the -basic transition metal to affect the reactivity of the dihapto-coordinated ligand. Alkylation isobserved at the heteroatom of the ketone and the nitrile, but depending on the reagent, alkylation of thenitrosyl ligand or addition to the complexed -bond also occurs. The structures of several nitriliumcomplexes and a rare example of an 2-acetonium complex are also reported.