Frech, C M; Blacque, O; Schmalle, H W; Berke, H (2006). Metal nitrosyl reactivity: Acetonitrile-promoted insertion of an alkylidene into a nitrosyl ligand with fission of the NO bond. Chemistry - A European Journal, 12(20):5199-5209.
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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(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)(OCNH)(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.
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|Item Type:||Journal Article, refereed|
|Communities & Collections:||07 Faculty of Science > Department of Chemistry|
|Date:||5 July 2006|
|Deposited On:||11 Feb 2008 12:25|
|Last Modified:||27 Nov 2013 19:17|
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