Title: Ligand controlled dioxygen oxidation of rhenium nitrosyl complexes
Authors : Frech, C. M.
Blacque, O.
Schmalle, H. W.
Berke, H.
Published in : Dalton transactions
Volume(Issue) : 35
Issue : 38
Pages : 4590
Pages to: 4598
Publisher / Ed. Institution : Royal Society of Chemistry
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: The addition of an excess of phenyldiazomethane to chlorobenzene solutions of the cationic dinitrosyl bisphosphine rhenium(-I) complexes [Re(NO)2(PR3)2][BAr(F)4] (R = Cy 1a, R = (i)Pr 1b) gave the corresponding benzylidene complexes [Re{=CH(C6H5)}(NO)2(PR3)2][BAr(F)4] (2a and 2b) in good yields. The treatment of 2b with dioxygen resulted in the oxidation of one of the nitrosyl ligands into the corresponding eta2-nitrito (3b) and nitrato complexes (4b) both in the solid state and in solution. In the case of the tricyclohexylphosphine derivative 2a the analogous conversion was not observed. A mechanism for the reaction of 2b with O2 is proposed which is based on an initial SET to the O2 molecule and subsequent formation of a peroxynitrite complex followed by the formation of a dinuclear mU-N2O4 intermediate. This in turn would undergo fission of the peroxo bond to afford 3b. A related sequence of steps is anticipated for the transformation of 3b to 4b. Furthermore, a similar mechanism seems reasonable for the seemingly topochemical reaction of 2b to 3b and 4b in the solid state. The initial SET to dioxygen and subsequent formation of the peroxynitrite complex is supported by DFT calculations on the trimethylphosphine model complexes [Re=CH{C6H5})(NO)2(PMe3)2]n+ (n = 1 and 2).
Departement: Life Sciences and Facility Management
Publication type: Article in scientific Journal
DOI : 10.1039/b604858g
ISSN: 1477-9226
1477-9234
URI: https://digitalcollection.zhaw.ch/handle/11475/10489
Appears in Collections:Publikationen Life Sciences und Facility Management

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