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.
Published in : Chemistry - a European journal
Volume(Issue) : 12
Issue : 20
Pages : 5199
Pages to: 5209
Publisher / Ed. Institution : Wiley
Issue Date: 2006
License (according to publishing contract) : Licence according to publishing contract
Type of review: Peer review (Publication)
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.
Departement: Life Sciences and Facility Management
Publication type: Article in scientific Journal
DOI : 10.1002/chem.200600286
ISSN: 0947-6539
URI: https://digitalcollection.zhaw.ch/handle/11475/10491
Appears in Collections:Publikationen Life Sciences und Facility Management

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