Issue 8, 2002

Amine–nitrile coupling in amino-monocarbollide complexes of molybdenum

Abstract

The Mo0 molybdenacarbaborane trianion [1-NH2-2,2,2-(CO)3-closo-2,1-MoCB10H10]3− is formed in situ from the reaction between [7-NH2-nido-7-CB10H10]3− and [Mo(CO)4{NH(CH2)5}2] in THF solution (THF = tetrahydrofuran). In the absence of nitriles, oxidation of this trianion by CH2[double bond, length as m-dash]CHCH2Br gives the MoII complex [1,2-μ-NH2-2,2,2-(CO)3-closo-2,1-MoCB10H10], isolated as its [N(PPh3)2]+ salt. However, in the presence of nitriles NCR, the same oxidation ultimately affords the species [N(PPh3)2][1,2-μ-{NHC(R)[double bond, length as m-dash]NH}-2,2,2-(CO)3-closo-2,1-MoCB10H10] in which amidine groups form a bridge between the carbon atom of the cage and the molybdenum, as a consequence of coupling of the nitrile with the cage-bound NH2 group. The acetamidine product [N(PPh3)2][1,2-μ-{NHC(Me)[double bond, length as m-dash]NH}-2,2,2-(CO)3-closo-2,1-MoCB10H10] is also formed by reaction of [7-NH2-nido-7-CB10H12] with [Mo(CO)6] in refluxing NCMe, and its structure was confirmed by an X-ray diffraction study. Further oxidation of this species by I2 in the presence of CNBut gives the MoIV derivatives [1,2-μ-{NHC(Me)[double bond, length as m-dash]NH}-2,2-(CNBut)2-2-L-2-I-closo-2,1-MoCB10H10] (L = CO, CNBut), of which the tris(isocyanide) complex has been studied by X-ray diffraction.

Graphical abstract: Amine–nitrile coupling in amino-monocarbollide complexes of molybdenum

Supplementary files

Article information

Article type
Paper
Submitted
19 Dec 2001
Accepted
13 Feb 2002
First published
20 Mar 2002

J. Chem. Soc., Dalton Trans., 2002, 1553-1558

Amine–nitrile coupling in amino-monocarbollide complexes of molybdenum

S. Du, J. A. Kautz, T. D. McGrath and F. G. A. Stone, J. Chem. Soc., Dalton Trans., 2002, 1553 DOI: 10.1039/B111562F

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