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Liang, F; Schmalle, H W; Berke, Heinz (2004). Insertion reactions of trans-Mo(dmpe)2(H)(NO) with imines. Inorganic Chemistry, 43(3):993-999.

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Abstract

The insertion chemistry of the hydride complex trans-Mo(dmpe)(2)(H)(NO) (1) (dmpe = bis(dimethylphosphino)ethane) with imines has been investigated. It was found that disubstituted aromatic imines RCH[double bond]NR' (R, R' = Ar) insert into the Mo-H bond of 1, while a series of various mono- and other disubstituted imines do not react. The insertion products trans-Mo(dmpe)(2)(NO)[NR'(CH(2)R)] (R = R' = Ph (2); R = Cp(2)Fe, R' = Ph (3); R = Ph, R' = Cp(2)Fe (4); R = 1-naphthyl, R' = Ph (5)) have been isolated and fully characterized by elemental analysis, IR and NMR spectroscopy, and mass spectrometry. The imine PhCH[double bond]NC(10)H(7) (C(10)H(7) = 1-naphthyl) reacted with 1 establishing an equilibrium to produce the nonisolable complex trans-Mo(dmpe)(2)(NO)[NC(10)H(7)(CH(2)Ph)] (6). The equilibrium constant for this reaction has been derived from VT-NMR measurements, and the Delta H and Delta S values of this reaction were calculated to be -48.8 +/- 0.4 kJ.mol(-1) and -33 +/- 1 J.K(-1).mol(-1) reflecting a mild exothermic process and its associative nature. Single-crystal X-ray diffraction analyses were carried out on 2-5.

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Additional indexing

Item Type:Journal Article, refereed
Communities & Collections:07 Faculty of Science > Department of Chemistry
DDC:540 Chemistry
Language:English
Date:9 February 2004
Deposited On:11 Feb 2008 12:25
Last Modified:28 Nov 2013 01:24
Publisher:American Chemical Society
ISSN:0020-1669
Publisher DOI:10.1021/ic030139l
PubMed ID:14753821

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