TY - JOUR
T1 - Syntheses, structures and redox properties of tris(pyrazolyl)borate-capped ruthenium vinyl complexes
AU - Farmer, J.D.
AU - Man, W.Y.
AU - Fox, M.A.
AU - Yufit, D.S.
AU - Howard, J.A.K.
AU - Hill, A.F.
AU - Low, Paul
PY - 2012/12/15
Y1 - 2012/12/15
N2 - Reaction of RuHCl(CO)(PPh3)3 with aryl alkynes HCtriple bond; length of mdashCC6H4R-4 [1: R = N(C6H4Me-4)2 (a), OMe (b), Me (c), CO2Me (d), NO2 (e)] gives the five-coordinate vinyl complexes Ru(CH=CHC6H4R-4)Cl(CO)(PPh3)2 (2a–e). Reaction of 2a with excess PMe3 gives crystallographically characterised Ru{CH=CHC6H4N(C6H4Me-4)2-4}Cl(CO)(PMe3)3 (3a), whilst reaction of 2a–e with KTp affords Ru(CHdouble bond; length as m-dashCHC6H4R-4)(CO)(PPh3)Tp (4a–e) bearing the facially capping Tp− ligand. Electrochemical and spectroelectochemical properties of 4a–e are consistent with substantial redox activity associated with the vinyl ligand, and these properties have been satisfactorily modelled by DFT based calculations of electronic structure.
AB - Reaction of RuHCl(CO)(PPh3)3 with aryl alkynes HCtriple bond; length of mdashCC6H4R-4 [1: R = N(C6H4Me-4)2 (a), OMe (b), Me (c), CO2Me (d), NO2 (e)] gives the five-coordinate vinyl complexes Ru(CH=CHC6H4R-4)Cl(CO)(PPh3)2 (2a–e). Reaction of 2a with excess PMe3 gives crystallographically characterised Ru{CH=CHC6H4N(C6H4Me-4)2-4}Cl(CO)(PMe3)3 (3a), whilst reaction of 2a–e with KTp affords Ru(CHdouble bond; length as m-dashCHC6H4R-4)(CO)(PPh3)Tp (4a–e) bearing the facially capping Tp− ligand. Electrochemical and spectroelectochemical properties of 4a–e are consistent with substantial redox activity associated with the vinyl ligand, and these properties have been satisfactorily modelled by DFT based calculations of electronic structure.
U2 - 10.1016/j.jorganchem.2012.09.001
DO - 10.1016/j.jorganchem.2012.09.001
M3 - Article
SN - 0022-328X
VL - 721-722
SP - 721
EP - 722
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
ER -