Solvent and phosphine dependency in the reaction of cis-RuCl2(P-P)(2) (P-P = dppm or dppe) with terminal alkynes

TY - JOUR

T1 - Solvent and phosphine dependency in the reaction of cis-RuCl2(P-P)(2) (P-P = dppm or dppe) with terminal alkynes

AU - Lynam, Jason M.

AU - Nixon, Tracy D.

AU - Whitwood, Adrian C.

PY - 2008/9/15

Y1 - 2008/9/15

N2 - Reaction of cis-[RuCl2(dppm)(2)] (dppm = 1,2-bis(diphenylphosphino) methane) with PhC CH and NaPF6 utilising methanol as solvent results in the formation of the eta(3)-butenynyl complex [Ru(eta(3)-PhC C-C=CHPh)(dppm)(2)][PF6] in good yield. Similar reactions with (BuC)-C-t CH and (PrC)-C-n CH resulted in the corresponding alkyl-substituted complexes and all three of these compounds have been characterised by NMR spectroscopy and X-ray crystallography. The mechanism of this reaction has been probed by employing labelling experiments with both PhC CD and PhC (CH)-C-13 allowing the identity of possible intermediates in the reaction to be determined. Furthermore, [Ru(eta(3)-PhC C-C=CHPh)(dppm)(2)][PF6] has been shown to be an effective regio- and stereo-selective catalyst for the dimerisation of PhC, CH to Z-PhC C-CH=CHPh in the absence of solvent. In contrast, no evidence for the formation of alkyne coupling was obtained from the reaction of cis-[RuCl2(dppm)(2)] (dppm = 1,2-bis(diphenylphosphino)methane) with PhC CH and NaPF6. (C) 2008 Elsevier B.V. All rights reserved.

AB - Reaction of cis-[RuCl2(dppm)(2)] (dppm = 1,2-bis(diphenylphosphino) methane) with PhC CH and NaPF6 utilising methanol as solvent results in the formation of the eta(3)-butenynyl complex [Ru(eta(3)-PhC C-C=CHPh)(dppm)(2)][PF6] in good yield. Similar reactions with (BuC)-C-t CH and (PrC)-C-n CH resulted in the corresponding alkyl-substituted complexes and all three of these compounds have been characterised by NMR spectroscopy and X-ray crystallography. The mechanism of this reaction has been probed by employing labelling experiments with both PhC CD and PhC (CH)-C-13 allowing the identity of possible intermediates in the reaction to be determined. Furthermore, [Ru(eta(3)-PhC C-C=CHPh)(dppm)(2)][PF6] has been shown to be an effective regio- and stereo-selective catalyst for the dimerisation of PhC, CH to Z-PhC C-CH=CHPh in the absence of solvent. In contrast, no evidence for the formation of alkyne coupling was obtained from the reaction of cis-[RuCl2(dppm)(2)] (dppm = 1,2-bis(diphenylphosphino)methane) with PhC CH and NaPF6. (C) 2008 Elsevier B.V. All rights reserved.

KW - ruthenium

KW - vinylidene

KW - mechanism

KW - RUTHENIUM HYDRIDE COMPLEXES

KW - ANTI-MARKOVNIKOV HYDRATION

KW - TO-HEAD DIMERIZATION

KW - STEREOSELECTIVE DIMERIZATION

KW - VINYLIDENE COMPLEXES

KW - METAL VINYLIDENES

KW - ORGANOMETALLIC CHEMISTRY

KW - CHELATING TRIPHOSPHINES

KW - MECHANISM

KW - CATALYSIS

UR - http://www.scopus.com/inward/record.url?scp=50449092675&partnerID=8YFLogxK

U2 - 10.1016/j.jorganchem.2008.06.021

DO - 10.1016/j.jorganchem.2008.06.021

M3 - Article

SN - 0022-328X

VL - 693

SP - 3103

EP - 3110

JO - JOURNAL OF ORGANOMETALLIC CHEMISTRY

JF - JOURNAL OF ORGANOMETALLIC CHEMISTRY

IS - 19

ER -