The synthesis, structure, reactivity and electrochemical properties of ruthenium complexes featuring cyanoacetylide ligands

Cordiner, R., Smith, M., Batsanov, A., Albesajove, D., Hartl, F. ORCID: https://orcid.org/0000-0002-7013-5360, Howard, J. and Low, P. (2006) The synthesis, structure, reactivity and electrochemical properties of ruthenium complexes featuring cyanoacetylide ligands. Inorganica Chimica Acta, 359 (3). pp. 946-961. ISSN 0020-1693 doi: 10.1016/j.ica.2005.06.044

Abstract/Summary

The complex [Ru(C&3bond; CC&3bond; N)(dppe)Cp*] (1) is readily obtained (ca. 70%) from the sequential reaction of [Ru(C=CH2)(dppe)Cp*]PF6 with (BuLi)-Bu-n and phenyl cyanate. The complex behaves as a typical transition metal acetylide upon reaction with tetracyanoethene, affording a metallated pentacyanobutadiene. Complex I is a useful metalloligand, and its reactions with [W(thf)(CO)5], [RuCl(PPh3)(2)Cp], [RuCl(dppe)Cp*] or cis-[RuCl2(dppe)(2)] all afforded products featuring the M-C&3bond; CC&3bond; N-M' motif, for which ground state structures indicate a degree of polarisation. Electrochemical and spectroelectrochemical studies reveal moderate interactions between the metal centres in the 35-electron dications [{Cp*(dppe)Ru}(mu-C&3bond; CC&3bond; N){RuL2Cp'}](2+) Ru(PPh3)(2)CP, Ru(dppe)Cp*).