Dinitrosyl rhenium complexes for ring-opening metathesis polymerization (ROMP)

Frech, Christian Manfred; Blacque, Olivier; Berke, Heinz

doi:10.1351/pac200678101877

Publication type:	Conference paper
Type of review:	Peer review (publication)
Title:	Dinitrosyl rhenium complexes for ring-opening metathesis polymerization (ROMP)
Authors:	Frech, Christian Manfred Blacque, Olivier Berke, Heinz
DOI:	10.1351/pac200678101877
Published in:	Pure and Applied Chemistry
Volume(Issue):	78
Issue:	10
Page(s):	1877
Pages to:	1887
Conference details:	International Symposium on Fine Chemistry and Functional Polymers (FCFP-XV) and the 1st International Symposium on Novel Materials and Synthesis (NMS-I), Shanghai, China, 17-20 October 2005
Issue Date:	2006
Publisher / Ed. Institution:	De Gruyter
Publisher / Ed. Institution:	Berlin
ISSN:	1365-3075 0033-4545
Language:	English
Subject (DDC):	540: Chemistry
Abstract:	The treatment of benzene solutions of the cations [Re(NO)2(PR3)2][BArF4] (R = Cy and R = iPr; [BArF4] = tetrakis{3,5-bis(trifluoromethyl)phenyl}borate) with phenyldiazomethane afforded the moderately stable cationic rhenium(I) benzylidene dinitrosyl bis(trialkyl) phosphine complexes as [BArF4]- salts in good yields. The cationic rhenium dinitrosyl bisphosphine complexes catalyze the ring-opening metathesis polymerization (ROMP) of highly strained nonfunctionalized cyclic olefins to give polymers with relatively high polydispersity indices, high molecular weights, and Z configurations of the double bonds in the polymer chain backbones of over 80 %. The benzylidene derivatives are almost inactive in ROMP catalysis with norbornene and in olefin metathesis. NMR experiments gave first hints for the initial formation of carbene complexes when [Re(NO)2(PR3)2][BArF4] was treated with norbornene. The carbene formation is initiated by an unique reaction sequence where the cleavage of the strained olefinic bond starts with phosphine migration forming a cyclic ylid carbene complex. The [2+2] addition of a norbornene molecule to the Re=C bond leads to the rhenacyclobutane complex, which is expected to be converted into an iminate complex by attack of the ylid function onto one of the NNO atoms followed by Wittig-type phosphine oxide elimination. The formation of phosphine oxide was confirmed by NMR spectroscopy. This species is thought to drive the ROMP metathesis with alternating rhenacyclobutane formations and cycloreversions. The proposed mechanism is supported by density functional theory (DFT) calculations.
URI:	https://digitalcollection.zhaw.ch/handle/11475/10488
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., & Berke, H. (2006). Dinitrosyl rhenium complexes for ring-opening metathesis polymerization (ROMP) [Conference paper]. Pure and Applied Chemistry, 78(10), 1877–1887. https://doi.org/10.1351/pac200678101877

Frech, C.M., Blacque, O. and Berke, H. (2006) ‘Dinitrosyl rhenium complexes for ring-opening metathesis polymerization (ROMP)’, in Pure and Applied Chemistry. Berlin: De Gruyter, pp. 1877–1887. Available at: https://doi.org/10.1351/pac200678101877.

C. M. Frech, O. Blacque, and H. Berke, “Dinitrosyl rhenium complexes for ring-opening metathesis polymerization (ROMP),” in Pure and Applied Chemistry, 2006, vol. 78, no. 10, pp. 1877–1887. doi: 10.1351/pac200678101877.

FRECH, Christian Manfred, Olivier BLACQUE und Heinz BERKE, 2006. Dinitrosyl rhenium complexes for ring-opening metathesis polymerization (ROMP). In: Pure and Applied Chemistry. Conference paper. Berlin: De Gruyter. 2006. S. 1877–1887

Frech, Christian Manfred, Olivier Blacque, and Heinz Berke. 2006. “Dinitrosyl Rhenium Complexes for Ring-Opening Metathesis Polymerization (ROMP).” Conference paper. In Pure and Applied Chemistry, 78:1877–87. Berlin: De Gruyter. https://doi.org/10.1351/pac200678101877.

Frech, Christian Manfred, et al. “Dinitrosyl Rhenium Complexes for Ring-Opening Metathesis Polymerization (ROMP).” Pure and Applied Chemistry, vol. 78, no. 10, De Gruyter, 2006, pp. 1877–87, https://doi.org/10.1351/pac200678101877.