TY - JOUR
T1 - Carbonyl substitution chemistry of some trimetallic transition metal cluster complexes with polyfunctional ligands
AU - Byrne, Lindsay T.
AU - Hondow, Nicole S.
AU - Koutsantonis, George A.
AU - Skelton, Brian W.
AU - Torabi, A. Asgar
AU - White, Allan H.
AU - Wild, S. Bruce
PY - 2008/5/1
Y1 - 2008/5/1
N2 - The trimetallic clusters [Ru3(CO)10(dppm)], [Ru3(CO)12] and [RuCo2(CO)11] react with a number of multifunctional secondary phosphine and tertiary arsine ligands to give products consequent on carbonyl substitution and, in the case of the secondary phosphines, PH activation. The reaction with the unresolved mixed P/S donor, 1-phenylphosphino-2-thio(ethane), HSCH2CH2PHPh ({double bond, long} LH2), gave two products under various conditions which have been characterised by spectroscopic and crystallographic means. These two complexes [Ru3(μ-dppm)(H)(CO)7(LH)] and [Ru3(μ-dppm)(H)(CO)8(LH)Ru3(μ-dpp m)(CO)9], show the versatility of the ligand, with it chelating in the former and bridging two Ru3 units in the latter. The stereogenic centres in the molecules gave rise to complicated spectroscopic data which are consistent with the presence of diastereoisomers. In the case of [Ru3(CO)12] the reaction with LH2 gave a poor yield of a tetranuclear butterfly cluster, [Ru4(CO)10(L)2], in which two of the ligands bridge opposite hinge wingtip bonds of the cluster. A related ligand, HSCH2CH2AsMe(C6H4CH 2OMe), reacted with [RuCo2(CO)11] to give a low yield of the heterobimetallic Ru-Co adduct, [RuCo(CO)6(SCH2CH2AsMe(C6H 4CH2OMe))], which appears to be the only one of its type so far structurally characterised. The secondary phosphine, HPMe(C6H4(CH2OMe)) and its oxide HP(O)Me(C6H4(CH2OMe)) also react with the cluster [Ru3(CO)10(dppm)] to give carbonyl substitution products, [Ru3(CO)5(dppm)(μ2-PMe(C6 H4CH2OMe))4], and [Ru3H(CO)7(dppm)(μ2,η 1-P({double bond, long}O)Me(C6H4CH2OMe))]. The former consists of an open Ru3 triangle with four phosphide ligands bridging the metal-metal bonds; the latter has the O atom symmetrically bridging one Ru-Ru bond, the P atom being attached to a non-bridged Ru atom.
AB - The trimetallic clusters [Ru3(CO)10(dppm)], [Ru3(CO)12] and [RuCo2(CO)11] react with a number of multifunctional secondary phosphine and tertiary arsine ligands to give products consequent on carbonyl substitution and, in the case of the secondary phosphines, PH activation. The reaction with the unresolved mixed P/S donor, 1-phenylphosphino-2-thio(ethane), HSCH2CH2PHPh ({double bond, long} LH2), gave two products under various conditions which have been characterised by spectroscopic and crystallographic means. These two complexes [Ru3(μ-dppm)(H)(CO)7(LH)] and [Ru3(μ-dppm)(H)(CO)8(LH)Ru3(μ-dpp m)(CO)9], show the versatility of the ligand, with it chelating in the former and bridging two Ru3 units in the latter. The stereogenic centres in the molecules gave rise to complicated spectroscopic data which are consistent with the presence of diastereoisomers. In the case of [Ru3(CO)12] the reaction with LH2 gave a poor yield of a tetranuclear butterfly cluster, [Ru4(CO)10(L)2], in which two of the ligands bridge opposite hinge wingtip bonds of the cluster. A related ligand, HSCH2CH2AsMe(C6H4CH 2OMe), reacted with [RuCo2(CO)11] to give a low yield of the heterobimetallic Ru-Co adduct, [RuCo(CO)6(SCH2CH2AsMe(C6H 4CH2OMe))], which appears to be the only one of its type so far structurally characterised. The secondary phosphine, HPMe(C6H4(CH2OMe)) and its oxide HP(O)Me(C6H4(CH2OMe)) also react with the cluster [Ru3(CO)10(dppm)] to give carbonyl substitution products, [Ru3(CO)5(dppm)(μ2-PMe(C6 H4CH2OMe))4], and [Ru3H(CO)7(dppm)(μ2,η 1-P({double bond, long}O)Me(C6H4CH2OMe))]. The former consists of an open Ru3 triangle with four phosphide ligands bridging the metal-metal bonds; the latter has the O atom symmetrically bridging one Ru-Ru bond, the P atom being attached to a non-bridged Ru atom.
KW - Carbonyl substitution
KW - Cluster
KW - Cobalt
KW - Ruthenium
KW - Secondary phosphine
KW - Thiol
UR - http://www.scopus.com/inward/record.url?scp=41949128613&partnerID=8YFLogxK
U2 - 10.1016/j.jorganchem.2008.01.040
DO - 10.1016/j.jorganchem.2008.01.040
M3 - Article
SN - 0022-328X
VL - 693
SP - 1738
EP - 1750
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 10
ER -