Syntheses, structures and redox properties of tris(pyrazolyl)borate-capped ruthenium vinyl complexes

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• 作者：Julian D. Farmer^a ; Wing Y. Man^a ; Mark A. Fox^a ; Dmitry S. Yufit^a ; Judith A.K. Howard^a ; Anthony F. Hill^b ; Paul J. Low^a ; ^{p.j.low@durham.ac.uk}
• 关键词：Ruthenium ; Vinyl ; Redox non-innocence ; Spectroelectrochemistry
• 刊名：Journal of Organometallic Chemistry
• 出版年：2012
• 出版时间：15 December, 2012
• 年：2012
• 卷：721-722
• 期：Complete
• 页码：173-185
• 全文大小：1097 K

文摘

Reaction of RuHCl(CO)(PPh₃)₃ with aryl alkynes HCCC₆H₄R-4 [1: R?=?N(C₆H₄Me-4)₂ (a), OMe (b), Me (c), CO₂Me (d), NO₂ (e)] gives the five-coordinate vinyl complexes Ru(CHCHC₆H₄R-4)Cl(CO)(PPh₃)₂ (2a-e). Reaction of 2a with excess PMe₃ gives crystallographically characterised Ru{CHCHC₆H₄N(C₆H₄Me-4)₂-4}Cl(CO)(PMe₃)₃ (3a), whilst reaction of 2a-e with KTp affords Ru(CHCHC₆H₄R-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.