Oxidative Dimerization of Arylalkynyl-Ruthenium Complexes

M.I. Bruce, A. Burgun, F. Gendron, G. Grelaud, J.F. Halet, Brian Skelton

Research output: Contribution to journalArticle

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Abstract

Chemical oxidation of Ru(C CPh)(PPh3)(2)Cp with [FeCp2]PF6 affords the binuclear cationic complexes [Cp(PPh3)(2)Ru{=C=CHC6H4CPh=C=}Ru(PPh3)(2)Cp] (PF6)(2) (2) and [Cp(PPh3)(2)Ru{C C(C6H4)CPh=C=}Ru(PPh3)(2)Cp]PF6 (3) by radical coupling at sites shown to be electron-rich by DFT studies, particularly involving the acetylide C-beta and C-para atoms and, to a lesser extent, the Cp carbon atoms. Complexes 2 and 3 are related by facile deprotonation/protonation reactions. When the 4-position of the Ph group is blocked, attack by C-beta upon the Cp group occurs to give the bis (vinylidene) [Ru{=C=C(C6H4Me-4)-eta-C5H4[Ru(PPh3)(2){=C=CH(C6H4Me-4)}(PPh3)(2) Cp]}](PF6)(2) (4), which can be deprotonated to give [Ru{=C=C(C6H4Me-4)-eta-CsH4[Ru(PPh3)(2){C C(C6H4Me-4)}(PPh3)(2)Cp]}]PF6 (5). Complex 4 is rapidly oxidized during workup to form [Ru{=C=C(C6H4Me)-eta-C5H4[Ru(CO)(PPh3)(2)]}(PPh3)(2)Cp](PF6)(2) (6). Single-crystal X-ray structure determinations of the salts 2, 3, and 6 are reported.
Original languageEnglish
Pages (from-to)2861-2868
JournalOrganometallics
Volume30
DOIs
Publication statusPublished - 2011

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Ruthenium
Dimerization
dimerization
ruthenium
Atoms
Deprotonation
Protonation
vinylidene
Carbon Monoxide
Discrete Fourier transforms
attack
atoms
Carbon
Salts
Single crystals
methylidyne
salts
X rays
Oxidation
oxidation

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Bruce, M. I., Burgun, A., Gendron, F., Grelaud, G., Halet, J. F., & Skelton, B. (2011). Oxidative Dimerization of Arylalkynyl-Ruthenium Complexes. Organometallics, 30, 2861-2868. https://doi.org/10.1021/om200213z
Bruce, M.I. ; Burgun, A. ; Gendron, F. ; Grelaud, G. ; Halet, J.F. ; Skelton, Brian. / Oxidative Dimerization of Arylalkynyl-Ruthenium Complexes. In: Organometallics. 2011 ; Vol. 30. pp. 2861-2868.
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title = "Oxidative Dimerization of Arylalkynyl-Ruthenium Complexes",
abstract = "Chemical oxidation of Ru(C CPh)(PPh3)(2)Cp with [FeCp2]PF6 affords the binuclear cationic complexes [Cp(PPh3)(2)Ru{=C=CHC6H4CPh=C=}Ru(PPh3)(2)Cp] (PF6)(2) (2) and [Cp(PPh3)(2)Ru{C C(C6H4)CPh=C=}Ru(PPh3)(2)Cp]PF6 (3) by radical coupling at sites shown to be electron-rich by DFT studies, particularly involving the acetylide C-beta and C-para atoms and, to a lesser extent, the Cp carbon atoms. Complexes 2 and 3 are related by facile deprotonation/protonation reactions. When the 4-position of the Ph group is blocked, attack by C-beta upon the Cp group occurs to give the bis (vinylidene) [Ru{=C=C(C6H4Me-4)-eta-C5H4[Ru(PPh3)(2){=C=CH(C6H4Me-4)}(PPh3)(2) Cp]}](PF6)(2) (4), which can be deprotonated to give [Ru{=C=C(C6H4Me-4)-eta-CsH4[Ru(PPh3)(2){C C(C6H4Me-4)}(PPh3)(2)Cp]}]PF6 (5). Complex 4 is rapidly oxidized during workup to form [Ru{=C=C(C6H4Me)-eta-C5H4[Ru(CO)(PPh3)(2)]}(PPh3)(2)Cp](PF6)(2) (6). Single-crystal X-ray structure determinations of the salts 2, 3, and 6 are reported.",
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Bruce, MI, Burgun, A, Gendron, F, Grelaud, G, Halet, JF & Skelton, B 2011, 'Oxidative Dimerization of Arylalkynyl-Ruthenium Complexes' Organometallics, vol. 30, pp. 2861-2868. https://doi.org/10.1021/om200213z

Oxidative Dimerization of Arylalkynyl-Ruthenium Complexes. / Bruce, M.I.; Burgun, A.; Gendron, F.; Grelaud, G.; Halet, J.F.; Skelton, Brian.

In: Organometallics, Vol. 30, 2011, p. 2861-2868.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Oxidative Dimerization of Arylalkynyl-Ruthenium Complexes

AU - Bruce, M.I.

AU - Burgun, A.

AU - Gendron, F.

AU - Grelaud, G.

AU - Halet, J.F.

AU - Skelton, Brian

PY - 2011

Y1 - 2011

N2 - Chemical oxidation of Ru(C CPh)(PPh3)(2)Cp with [FeCp2]PF6 affords the binuclear cationic complexes [Cp(PPh3)(2)Ru{=C=CHC6H4CPh=C=}Ru(PPh3)(2)Cp] (PF6)(2) (2) and [Cp(PPh3)(2)Ru{C C(C6H4)CPh=C=}Ru(PPh3)(2)Cp]PF6 (3) by radical coupling at sites shown to be electron-rich by DFT studies, particularly involving the acetylide C-beta and C-para atoms and, to a lesser extent, the Cp carbon atoms. Complexes 2 and 3 are related by facile deprotonation/protonation reactions. When the 4-position of the Ph group is blocked, attack by C-beta upon the Cp group occurs to give the bis (vinylidene) [Ru{=C=C(C6H4Me-4)-eta-C5H4[Ru(PPh3)(2){=C=CH(C6H4Me-4)}(PPh3)(2) Cp]}](PF6)(2) (4), which can be deprotonated to give [Ru{=C=C(C6H4Me-4)-eta-CsH4[Ru(PPh3)(2){C C(C6H4Me-4)}(PPh3)(2)Cp]}]PF6 (5). Complex 4 is rapidly oxidized during workup to form [Ru{=C=C(C6H4Me)-eta-C5H4[Ru(CO)(PPh3)(2)]}(PPh3)(2)Cp](PF6)(2) (6). Single-crystal X-ray structure determinations of the salts 2, 3, and 6 are reported.

AB - Chemical oxidation of Ru(C CPh)(PPh3)(2)Cp with [FeCp2]PF6 affords the binuclear cationic complexes [Cp(PPh3)(2)Ru{=C=CHC6H4CPh=C=}Ru(PPh3)(2)Cp] (PF6)(2) (2) and [Cp(PPh3)(2)Ru{C C(C6H4)CPh=C=}Ru(PPh3)(2)Cp]PF6 (3) by radical coupling at sites shown to be electron-rich by DFT studies, particularly involving the acetylide C-beta and C-para atoms and, to a lesser extent, the Cp carbon atoms. Complexes 2 and 3 are related by facile deprotonation/protonation reactions. When the 4-position of the Ph group is blocked, attack by C-beta upon the Cp group occurs to give the bis (vinylidene) [Ru{=C=C(C6H4Me-4)-eta-C5H4[Ru(PPh3)(2){=C=CH(C6H4Me-4)}(PPh3)(2) Cp]}](PF6)(2) (4), which can be deprotonated to give [Ru{=C=C(C6H4Me-4)-eta-CsH4[Ru(PPh3)(2){C C(C6H4Me-4)}(PPh3)(2)Cp]}]PF6 (5). Complex 4 is rapidly oxidized during workup to form [Ru{=C=C(C6H4Me)-eta-C5H4[Ru(CO)(PPh3)(2)]}(PPh3)(2)Cp](PF6)(2) (6). Single-crystal X-ray structure determinations of the salts 2, 3, and 6 are reported.

U2 - 10.1021/om200213z

DO - 10.1021/om200213z

M3 - Article

VL - 30

SP - 2861

EP - 2868

JO - Organometallics

JF - Organometallics

SN - 0276-7333

ER -