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https://hdl.handle.net/2440/61388
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Type: | Journal article |
Title: | Some reactions of an eta(3)-tetracyanobutadienyl-ruthenium complex |
Author: | Bruce, M. Fox, M. Low, P. Skelton, B. Zaitseva, N. |
Citation: | Dalton Transactions: an international journal of inorganic chemistry, 2010; 39(15):3759-3770 |
Publisher: | Royal Soc Chemistry |
Issue Date: | 2010 |
ISSN: | 1477-9226 1477-9234 |
Statement of Responsibility: | Michael I. Bruce, Mark A. Fox, Paul J. Low, Brian W. Skelton and Natasha N. Zaitseva |
Abstract: | In the eta(3)-butadienyl complex Ru{eta(3)-C(CN)(2)CPhC=C(CN)(2)}(PPh(3))Cp 1, which is formed from Ru(C[triple bond]CPh)(PPh(3))(2)Cp and tcne, a CN group reacts with MeO(-) to give the methoxy-amide Ru{NH=C(OMe)C(CN)=CCPh=C(CN)(2)}(PPh(3))Cp 2, in which the NH has displaced the C=C from the Ru centre with formation of a RuC(3)N ring. "Click addition" of azide to a CN group in 1 gives the oligomeric tetrazolato complex Ru{N(3)N[Na(OEt(2))]=CC(CN)=CCPh=C(CN)(2)}(PPh(3))Cp 3, also containing a RuC(3)N ring. Salt-elimination reactions of 3 with MeOTf, FeCl(dppe)Cp, RuCl(dppe)Cp* and trans-PtCl(2){P(tol)(3)}(2) result in selective substitution at one nitrogen atom of the RuC(3)N ring. Geometries of 1 and the anion in 3 were computed by DFT methods. Preferences for CN groups attacked in the nucleophilic and cycloaddition reactions of 1 are supported by NBO calculations. Alkylation of 1 in reactions with 1,2-dimethoxyethane gave two isomers of Ru{N(3)[CH(CH(2)OMe)(OMe)]N=CC(CN)=CCPh=C(CN)(2)}(PPh(3))Cp 8 and 9, differing in the sites of attachment of the alkyl group, likely by radical processes. The molecular structures of eight complexes are reported, including a re-determination of 1. Computed NMR chemical shifts are used to reassign the butadienyl carbon resonances in the (13)C NMR spectrum of 1. |
Keywords: | Ruthenium Organometallic Compounds Crystallography, X-Ray Spectrophotometry, Infrared Magnetic Resonance Spectroscopy Molecular Conformation Thermodynamics Coordination Complexes |
Rights: | © Royal Society of Chemistry 2010 |
DOI: | 10.1039/b921324d |
Grant ID: | ARC |
Published version: | http://dx.doi.org/10.1039/b921324d |
Appears in Collections: | Aurora harvest Chemistry and Physics publications |
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