Metal nitrosyl reactivity : acetonitrile-promoted insertion of an alkylidene into a nitrosyl ligand with fission of the NO bond

Frech, C. M.; Blacque, O.; Schmalle, H. W.; Berke, H.

doi:10.1002/chem.200600286

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
Page(s):	5199
Pages to:	5209
Issue Date:	2006
Publisher / Ed. Institution:	Wiley
ISSN:	0947-6539 1521-3765
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.
URI:	https://digitalcollection.zhaw.ch/handle/11475/10491
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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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. https://doi.org/10.1002/chem.200600286

Frech, C.M. et al. (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), pp. 5199–5209. Available at: https://doi.org/10.1002/chem.200600286.

C. M. Frech, O. Blacque, H. W. Schmalle, and H. Berke, “Metal nitrosyl reactivity : acetonitrile-promoted insertion of an alkylidene into a nitrosyl ligand with fission of the NO bond,” Chemistry - A European Journal, vol. 12, no. 20, pp. 5199–5209, 2006, doi: 10.1002/chem.200600286.

FRECH, C. M., O. BLACQUE, H. W. SCHMALLE und H. BERKE, 2006. Metal nitrosyl reactivity : acetonitrile-promoted insertion of an alkylidene into a nitrosyl ligand with fission of the NO bond. Chemistry - A European Journal. 2006. Bd. 12, Nr. 20, S. 5199–5209. DOI 10.1002/chem.200600286

Frech, C. M., O. Blacque, H. W. Schmalle, and H. Berke. 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. https://doi.org/10.1002/chem.200600286.

Frech, C. M., et al. “Metal Nitrosyl Reactivity : Acetonitrile-Promoted Insertion of an Alkylidene into a Nitrosyl Ligand with Fission of the NO Bond.” Chemistry - A European Journal, vol. 12, no. 20, 2006, pp. 5199–209, https://doi.org/10.1002/chem.200600286.