Reactions of tetranuclear rhodium-triruthenium clusters with di- and tri-phosphines and with alkynes

Jean L. Le Grand, W. Edward Lindsell, Kevin J. McCullough, Calum H. McIntosh, A. Gavin Meiklejohn

Research output: Contribution to journalArticle

Abstract

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.

Original languageEnglish
Pages (from-to)1089-1099
Number of pages11
JournalJournal of the Chemical Society, Dalton Transactions
Issue number6
DOIs
Publication statusPublished - 1992

Fingerprint

Phosphines
Rhodium
Alkynes
Carbon Monoxide
phosphine
Ruthenium
Methylene Chloride

Cite this

Le Grand, Jean L. ; Lindsell, W. Edward ; McCullough, Kevin J. ; McIntosh, Calum H. ; Meiklejohn, A. Gavin. / Reactions of tetranuclear rhodium-triruthenium clusters with di- and tri-phosphines and with alkynes. In: Journal of the Chemical Society, Dalton Transactions. 1992 ; No. 6. pp. 1089-1099.
@article{c91e16b1f84741a6a71ed5311e73c893,
title = "Reactions of tetranuclear rhodium-triruthenium clusters with di- and tri-phosphines and with alkynes",
abstract = "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) {\AA}, {\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.",
author = "{Le Grand}, {Jean L.} and Lindsell, {W. Edward} and McCullough, {Kevin J.} and McIntosh, {Calum H.} and Meiklejohn, {A. Gavin}",
year = "1992",
doi = "10.1039/DT9920001089",
language = "English",
pages = "1089--1099",
journal = "Journal of the Chemical Society, Dalton Transactions",
issn = "1472-7773",
number = "6",

}

Reactions of tetranuclear rhodium-triruthenium clusters with di- and tri-phosphines and with alkynes. / Le Grand, Jean L.; Lindsell, W. Edward; McCullough, Kevin J.; McIntosh, Calum H.; Meiklejohn, A. Gavin.

In: Journal of the Chemical Society, Dalton Transactions, No. 6, 1992, p. 1089-1099.

Research output: Contribution to journalArticle

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

SP - 1089

EP - 1099

JO - Journal of the Chemical Society, Dalton Transactions

JF - Journal of the Chemical Society, Dalton Transactions

SN - 1472-7773

IS - 6

ER -