TY - JOUR
T1 - Reactions of tetranuclear rhodium-triruthenium clusters with di- and tri-phosphines and with alkynes
AU - Le Grand, Jean L.
AU - Lindsell, W. Edward
AU - McCullough, Kevin J.
AU - McIntosh, Calum H.
AU - Meiklejohn, A. Gavin
PY - 1992
Y1 - 1992
N2 - The compound [RhRu3(µ-H)2(µ-CO)(CO)9(cp)] 1 (cp = ?5-C2H5) and an equimolar amount of diphosphine Ph2P(CH2)nPPh2 [n = 1 (dppm), 2 (dppe) or 3 (dppp)] react at ambient temperature principally with cleavage of the heteronuclear cluster to form several homonuclear rhodium and ruthenium products. Isolated ruthenium clusters are simple phosphine derivatives of [Ru3(CO)12] or [Ru4(µ-H)4(CO)12], including [Ru3(µ-diphos)2(CO)8] (diphos = dppm or dppe), [Ru3(µ-diphos)(CO)10] and [{Ru3(µ-diphos)(CO)9}2(µ-diphos)] (diphos = dppe or dppp), and [Ru4(µ-H)4(CO)10(dppp)]. Reaction of 1 with the triphosphine MeC(CH2PPh2)3 affords hydrido-clusters [Ru3(µ-H)H(µ-triphos)(CO)8] and [Ru3(µ-H){µ-PPhCH2CMe(CH2PPh 2)2(CO)8] 12, the latter formed by elimination of benzene under very mild reaction conditions. The solid-state structure of cluster 12 has been determined by X-ray crystallographic analysis [monosolvate with dichloromethane, monoclinic, space group P21/n, a = 19.549(3), b = 14.2462(21), c = 16.429(4) Å, ß = 90.271(18)°, Z = 4, R = 0.051, R' = 0.060] and the geometrical non-rigidity of this asymmetric molecule in solution is revealed by variable-temperature 31P NMR spectroscopy. Reactions of cluster 1 with alkynes, RC=CR (R = Ph or Et), give heteronuclear products, including isomers of [RhRu3(C2R2)(CO)9(cp)] and trimetallic clusters [RhRu2(C2R2)(CO)n(cp)] (R = Et, n = 7; R = Ph, n = 8); from reaction of [RhRu3(µ-H)4(CO)9(?5-C 5Me5)] with PhC=CPh a related tetranuclear cluster [RhRu3(C2R2)(CO)9(? 5-C5Me5)] is formed. A new, octahedral heteronuclear cluster [Rh2Ru4(µ-H)2(CO)12(cp) 2] is also reported.
AB - The compound [RhRu3(µ-H)2(µ-CO)(CO)9(cp)] 1 (cp = ?5-C2H5) and an equimolar amount of diphosphine Ph2P(CH2)nPPh2 [n = 1 (dppm), 2 (dppe) or 3 (dppp)] react at ambient temperature principally with cleavage of the heteronuclear cluster to form several homonuclear rhodium and ruthenium products. Isolated ruthenium clusters are simple phosphine derivatives of [Ru3(CO)12] or [Ru4(µ-H)4(CO)12], including [Ru3(µ-diphos)2(CO)8] (diphos = dppm or dppe), [Ru3(µ-diphos)(CO)10] and [{Ru3(µ-diphos)(CO)9}2(µ-diphos)] (diphos = dppe or dppp), and [Ru4(µ-H)4(CO)10(dppp)]. Reaction of 1 with the triphosphine MeC(CH2PPh2)3 affords hydrido-clusters [Ru3(µ-H)H(µ-triphos)(CO)8] and [Ru3(µ-H){µ-PPhCH2CMe(CH2PPh 2)2(CO)8] 12, the latter formed by elimination of benzene under very mild reaction conditions. The solid-state structure of cluster 12 has been determined by X-ray crystallographic analysis [monosolvate with dichloromethane, monoclinic, space group P21/n, a = 19.549(3), b = 14.2462(21), c = 16.429(4) Å, ß = 90.271(18)°, Z = 4, R = 0.051, R' = 0.060] and the geometrical non-rigidity of this asymmetric molecule in solution is revealed by variable-temperature 31P NMR spectroscopy. Reactions of cluster 1 with alkynes, RC=CR (R = Ph or Et), give heteronuclear products, including isomers of [RhRu3(C2R2)(CO)9(cp)] and trimetallic clusters [RhRu2(C2R2)(CO)n(cp)] (R = Et, n = 7; R = Ph, n = 8); from reaction of [RhRu3(µ-H)4(CO)9(?5-C 5Me5)] with PhC=CPh a related tetranuclear cluster [RhRu3(C2R2)(CO)9(? 5-C5Me5)] is formed. A new, octahedral heteronuclear cluster [Rh2Ru4(µ-H)2(CO)12(cp) 2] is also reported.
UR - http://www.scopus.com/inward/record.url?scp=37049085113&partnerID=8YFLogxK
U2 - 10.1039/DT9920001089
DO - 10.1039/DT9920001089
M3 - Article
SN - 1472-7773
SP - 1089
EP - 1099
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 6
ER -