Some reactions of an eta(3)-tetracyanobutadienyl-ruthenium complex

Bruce, Michael I.; Fox, Mark A.; Low, Paul J.; Skelton, Brian W.; Zaitseva, Natasha N.

Abstract

In the η3-butadienyl complex Ru{η3-C(CN)2CPhC[double bond, length as m-dash]C(CN)2}(PPh3)Cp 1, which is formed from Ru(C[triple bond, length as m-dash]CPh)(PPh3)2Cp and tcne, a CN group reacts with MeO− to give the methoxy-amide Ru{NH[double bond, length as m-dash]C(OMe)C(CN)[double bond, length as m-dash]CCPh[double bond, length as m-dash]C(CN)2}(PPh3)Cp 2, in which the NH has displaced the C[double bond, length as m-dash]C from the Ru centre with formation of a RuC3N ring. “Click addition” of azide to a CN group in 1 gives the oligomeric tetrazolato complex Ru{N3N[Na(OEt2)][double bond, length as m-dash]CC(CN)[double bond, length as m-dash]CCPh[double bond, length as m-dash]C(CN)2}(PPh3)Cp 3, also containing a RuC3N ring. Salt-elimination reactions of 3 with MeOTf, FeCl(dppe)Cp, RuCl(dppe)Cp* and trans-PtCl2{P(tol)3}2 result in selective substitution at one nitrogen atom of the RuC3N 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{N3[CH(CH2OMe)(OMe)]N[double bond, length as m-dash]CC(CN)[double bond, length as m-dash]CCPh[double bond, length as m-dash]C(CN)2}(PPh3)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 13C NMR spectrum of 1.

Citation

Bruce, M. I., Fox, M. A., Low, P. J., Skelton, B. W., & Zaitseva, N. N. (2010). Some reactions of an eta(3)-tetracyanobutadienyl-ruthenium complex. Dalton Transactions, 39(15), 3759-3770. https://doi.org/10.1039/b921324d

• Journal Article Type: Article
• Publication Date: Apr 21, 2010
• Deposit Date: Dec 14, 2011
• Journal: Dalton Transactions
• Print ISSN: 1477-9226
• Electronic ISSN: 1477-9234
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 39
• Issue: 15
• Pages: 3759-3770
• DOI: https://doi.org/10.1039/b921324d
• Public URL: https://durham-repository.worktribe.com/output/1533027