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Platinum-mediated dinitrogen liberation from 2-picolyl azide through a putative Pt═N double bond containing intermediate.

Authors
Type
Published Article
Journal
Inorganic Chemistry
1520-510X
Publisher
American Chemical Society
Publication Date
Volume
52
Issue
8
Pages
4528–4533
Identifiers
DOI: 10.1021/ic302834e
PMID: 23534346
Source
Medline
License
Unknown

Abstract

2-Picolyl azide reacts with cis-[PtCl2(DMSO)2] to form the diimino complex [Pt(II)Cl2{NH═C(H)Py}] with subsequent dinitrogen liberation. The formation of the latter complex is scrutinized in a combined experimental and theoretical analysis. We establish in silico that the transformation involves a highly reactive intermediate containing a Pt═N double bond formed after the extrusion of N2 from the azide functionality. The prerequisites for N2 liberation and for the stabilization of the nitrene-related intermediate are analyzed in detail.

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