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

Julian D. Farmer; Wing Y. Man; Mark A. Fox; Dmitry S. Yufit; Judith A.K. Howard; Anthony F. Hill; Paul J. Low

doi:10.1016/j.jorganchem.2012.09.001

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

Julian D. Farmer, Wing Y. Man, Mark A. Fox, Dmitry S. Yufit, Judith A.K. Howard, Anthony F. Hill, Paul J. Low^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

4 Citations (Scopus)

Abstract

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(CHCHC₆H ₄R-4)Cl(CO)(PPh₃)₂ (2a-e). Reaction of 2a with excess PMe₃ gives crystallographically characterised Ru{CHCHC ₆H₄N(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.

Original language	English
Pages (from-to)	173-185
Number of pages	13
Journal	Journal of Organometallic Chemistry
Volume	721-722
DOIs	https://doi.org/10.1016/j.jorganchem.2012.09.001
Publication status	Published - 15 Dec 2012

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@article{ffb2319327e24f6fa141786086727d83,

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

abstract = "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(CHCHC6H 4R-4)Cl(CO)(PPh3)2 (2a-e). Reaction of 2a with excess PMe3 gives crystallographically characterised Ru\{CHCHC 6H4N(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.",

keywords = "Redox non-innocence, Ruthenium, Spectroelectrochemistry, Vinyl",

author = "Farmer, \{Julian D.\} and Man, \{Wing Y.\} and Fox, \{Mark A.\} and Yufit, \{Dmitry S.\} and Howard, \{Judith A.K.\} and Hill, \{Anthony F.\} and Low, \{Paul J.\}",

year = "2012",

month = dec,

day = "15",

doi = "10.1016/j.jorganchem.2012.09.001",

language = "English",

volume = "721-722",

pages = "173--185",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

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T1 - Syntheses, structures and redox properties of tris(pyrazolyl)borate-capped ruthenium vinyl complexes

AU - Farmer, Julian D.

AU - Man, Wing Y.

AU - Fox, Mark A.

AU - Yufit, Dmitry S.

AU - Howard, Judith A.K.

AU - Hill, Anthony F.

AU - Low, Paul J.

PY - 2012/12/15

Y1 - 2012/12/15

N2 - 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(CHCHC6H 4R-4)Cl(CO)(PPh3)2 (2a-e). Reaction of 2a with excess PMe3 gives crystallographically characterised Ru{CHCHC 6H4N(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.

AB - 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(CHCHC6H 4R-4)Cl(CO)(PPh3)2 (2a-e). Reaction of 2a with excess PMe3 gives crystallographically characterised Ru{CHCHC 6H4N(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.

KW - Redox non-innocence

KW - Ruthenium

KW - Spectroelectrochemistry

KW - Vinyl

UR - https://www.scopus.com/pages/publications/84869503251

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 - 173

EP - 185

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

ER -

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

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