Publication type: Article in scientific journal
Type of review: Peer review (publication)
Title: Metal nitrosyl reactivity : acetonitrile-promoted insertion of an alkylidene into a nitrosyl ligand with fission of the NO bond
Authors: Frech, C. M.
Blacque, O.
Schmalle, H. W.
Berke, H.
DOI: 10.1002/chem.200600286
Published in: Chemistry - A European Journal
Volume(Issue): 12
Issue: 20
Pages: 5199
Pages to: 5209
Issue Date: 2006
Publisher / Ed. Institution: Wiley
ISSN: 0947-6539
Language: English
Subject (DDC): 540: Chemistry
Abstract: Treatment of the complexes [Re(NO)2(PR3)2][BAr(F)4] (R = Cy, 1 a; R = iPr, 1 b) with phenyldiazomethane gave the cationic benzylidene species [Re{CH(C6H5)}(NO)2(PR3)2][BAr(F)4] (2 a and 2 b) in good yields. Upon reaction of 2 a and 2 b with acetonitrile, the consecutive formation of [Re(N[triple bond]CCH3)(N[triple bond]CPh)(NO)(OC(CH3)=NH)(PR3)][BAr(F)4] (3 a and 3 b) and [Re(NCCH3)(OC{CH3}NH{C6H5})(NO)(PR3)2][BAr(F)4] (4 a and 4 b) was observed. The proposed reaction sequence involves the coupling of coordinated NO, carbene and acetonitrile molecules to yield the (1Z)-N-[imino(phenyl)methyl]ethanimidate ligand. The coupling of the nitrosyl and the benzylidene is anticipated to occur first, forming an oximate species. The subsequent acetonitrile addition can be envisaged as a heteroene reaction of the oximate and the acetonitrile ligand yielding 3 a and 3 b, which in turn can cyclise and undergo a prototropic shift initiated by an internal attack of the ethaneimidate ligand on the benzonitrile moiety to afford 4 a and 4 b.
Fulltext version: Published version
License (according to publishing contract): Licence according to publishing contract
Departement: Life Sciences and Facility Management
Appears in collections:Publikationen Life Sciences und Facility Management

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