Ligand controlled dioxygen oxidation of rhenium nitrosyl complexes

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

doi:10.1039/b604858g

Publication type:	Article in scientific journal
Type of review:	Peer review (publication)
Title:	Ligand controlled dioxygen oxidation of rhenium nitrosyl complexes
Authors:	Frech, C. M. Blacque, O. Schmalle, H. W. Berke, H.
DOI:	10.1039/b604858g
Published in:	Dalton Transactions
Volume(Issue):	35
Issue:	38
Page(s):	4590
Pages to:	4598
Issue Date:	2006
Publisher / Ed. Institution:	Royal Society of Chemistry
ISSN:	1477-9226 1477-9234
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).
URI:	https://digitalcollection.zhaw.ch/handle/11475/10489
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). Ligand controlled dioxygen oxidation of rhenium nitrosyl complexes. Dalton Transactions, 35(38), 4590–4598. https://doi.org/10.1039/b604858g

Frech, C.M. et al. (2006) ‘Ligand controlled dioxygen oxidation of rhenium nitrosyl complexes’, Dalton Transactions, 35(38), pp. 4590–4598. Available at: https://doi.org/10.1039/b604858g.

C. M. Frech, O. Blacque, H. W. Schmalle, and H. Berke, “Ligand controlled dioxygen oxidation of rhenium nitrosyl complexes,” Dalton Transactions, vol. 35, no. 38, pp. 4590–4598, 2006, doi: 10.1039/b604858g.

FRECH, C. M., O. BLACQUE, H. W. SCHMALLE und H. BERKE, 2006. Ligand controlled dioxygen oxidation of rhenium nitrosyl complexes. Dalton Transactions. 2006. Bd. 35, Nr. 38, S. 4590–4598. DOI 10.1039/b604858g

Frech, C. M., O. Blacque, H. W. Schmalle, and H. Berke. 2006. “Ligand Controlled Dioxygen Oxidation of Rhenium Nitrosyl Complexes.” Dalton Transactions 35 (38): 4590–98. https://doi.org/10.1039/b604858g.

Frech, C. M., et al. “Ligand Controlled Dioxygen Oxidation of Rhenium Nitrosyl Complexes.” Dalton Transactions, vol. 35, no. 38, 2006, pp. 4590–98, https://doi.org/10.1039/b604858g.