TY - JOUR
T1 - Use of the cationic fragments [Ru(η5-C5H 5)(MeCN)3]+ and [M(η6-C 6H5R)(MeCN)3]+ (M=Os, Ru; R=H, Me) as ionic coupling reagents with the anions
AU - Al-Mandhary, Muna R.A.
AU - Buntem, Radchada
AU - Cathey, Christopher
AU - Lewis, Jack
AU - De Arellano, M. Carmen Ramirez
AU - Shields, Gregory P.
AU - Doherty, Cheryl L.
AU - Raithby, Paul R.
N1 - Funding Information:
The authors thank The Government of the Sultanate of Oman (M.R.A.A), The Overseas Research Students Awards (M.R.A.A.), The Cambridge Thai Trust (R.B.), the E.P.S.R.C (C.C., G.P.S.) and the Cambridge Crystallographic Data Centre (G.P.S.) for funding, the EU for a Human Capital and Mobility Grant (M.C.R. de A.) and Johnson Matthey PLC for the generous loan of Os and Ru salts. We are grateful to the University of Bath for a University Studentship (C.L.D.).
PY - 2003/7/4
Y1 - 2003/7/4
N2 - The cluster [H2Os4(CO)13] may be reduced with K/Ph2CO to generate an anion which reacts with [M(η 6-C6H5R)(MeCN)3]2+ (M=Os, Ru; R=H, Me) affording the capped clusters [H2Os4M(CO) 12(η6-C6H5R)] (M=Os, R=H (1); M=Ru, R=H (2); M=Os, R=Me (3)) with the arene ligand on one of the axial site of a trigonal bipyramid. The Os clusters 1 and 3 transform into the more stable equatorial isomers, 4 and 5, respectively, in 24 h. The structure of 5 has been confirmed by a single crystal X-ray diffraction study, and all the complexes have been characterised spectroscopically. The axial isomers may be carbonylated or hydrogenated to generate the edge-bridged tetrahedral clusters [H2Os4M(CO)13(η6-C 6H5R)] (M=Os, R=H (6); M=Ru, R=H (7); M=Os, R=Me (8)) and the known clusters [H4Os4M(CO)12(η 6-C6H6)] (M=Os (9); Ru (10)). The structure of 7 has been confirmed by an X-ray diffraction analysis. The axial isomer 1 reacts with PPh2Me to yield the addition product [H 2Os5(CO)12(η6-C 6H6)PPh2Me] (11), whereas the mixed osmium-ruthenium analogue undergoes a transformation to the 'spiked' tetrahedral [H3Os4Ru(CO)12(μ 3-σ,σ,η6-C6H 5)PPh2Me] (12). Deprotonation of the axial isomers 1 and 2 and subsequent reaction with [AuPPh3]+ yields [HOs 4M(CO)12(C6H6)(AuPPh3)] (M=Os (13); Ru (14)). As well as spectroscopic characterisation cluster, the structures of 11, 12 and 13 have been established by X-ray diffraction experiments. In a related series of reactions the cluster monoanion [Os 4(CO)13X]- (X=Cl (15), Br (16), I (17)) may be capped using the monocation [Ru(η5-C5H 5)(MeCN)3]+ affording [HOs4Ru(CO) 13(η5-C5H5)] (18), which is readily deprotonated and further capped with [AuPPh3]+ to afford the neutral cluster [Os4(CO)13Ru(η 5-C5H5)AuPPh3] (20). The structures of 15, 18 and 20 have been established crystallographically. The cluster anion [Os4(CO)13X]- may be reduced with K/Ph 2CO and the resulting anionic complex coupled with [Ru(η 5-C5H5)(MeCN)3]+, providing another route to [Os4Ru(CO)13(η 5-C5H5)]- (19). This anionic complex may also be coupled with [Ru(η6-C6H 6)(MeCN)3]2+ affording [Os4Ru(CO) 13(η6-C6H6)] (21) which has also been structurally characterised.
AB - The cluster [H2Os4(CO)13] may be reduced with K/Ph2CO to generate an anion which reacts with [M(η 6-C6H5R)(MeCN)3]2+ (M=Os, Ru; R=H, Me) affording the capped clusters [H2Os4M(CO) 12(η6-C6H5R)] (M=Os, R=H (1); M=Ru, R=H (2); M=Os, R=Me (3)) with the arene ligand on one of the axial site of a trigonal bipyramid. The Os clusters 1 and 3 transform into the more stable equatorial isomers, 4 and 5, respectively, in 24 h. The structure of 5 has been confirmed by a single crystal X-ray diffraction study, and all the complexes have been characterised spectroscopically. The axial isomers may be carbonylated or hydrogenated to generate the edge-bridged tetrahedral clusters [H2Os4M(CO)13(η6-C 6H5R)] (M=Os, R=H (6); M=Ru, R=H (7); M=Os, R=Me (8)) and the known clusters [H4Os4M(CO)12(η 6-C6H6)] (M=Os (9); Ru (10)). The structure of 7 has been confirmed by an X-ray diffraction analysis. The axial isomer 1 reacts with PPh2Me to yield the addition product [H 2Os5(CO)12(η6-C 6H6)PPh2Me] (11), whereas the mixed osmium-ruthenium analogue undergoes a transformation to the 'spiked' tetrahedral [H3Os4Ru(CO)12(μ 3-σ,σ,η6-C6H 5)PPh2Me] (12). Deprotonation of the axial isomers 1 and 2 and subsequent reaction with [AuPPh3]+ yields [HOs 4M(CO)12(C6H6)(AuPPh3)] (M=Os (13); Ru (14)). As well as spectroscopic characterisation cluster, the structures of 11, 12 and 13 have been established by X-ray diffraction experiments. In a related series of reactions the cluster monoanion [Os 4(CO)13X]- (X=Cl (15), Br (16), I (17)) may be capped using the monocation [Ru(η5-C5H 5)(MeCN)3]+ affording [HOs4Ru(CO) 13(η5-C5H5)] (18), which is readily deprotonated and further capped with [AuPPh3]+ to afford the neutral cluster [Os4(CO)13Ru(η 5-C5H5)AuPPh3] (20). The structures of 15, 18 and 20 have been established crystallographically. The cluster anion [Os4(CO)13X]- may be reduced with K/Ph 2CO and the resulting anionic complex coupled with [Ru(η 5-C5H5)(MeCN)3]+, providing another route to [Os4Ru(CO)13(η 5-C5H5)]- (19). This anionic complex may also be coupled with [Ru(η6-C6H 6)(MeCN)3]2+ affording [Os4Ru(CO) 13(η6-C6H6)] (21) which has also been structurally characterised.
KW - Arene
KW - Carbonyl
KW - Cluster
KW - Crystal structures
KW - Cyclopentadiene
KW - Gold
KW - Osmium
KW - Ruthenium
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U2 - 10.1016/S0020-1693(02)01516-5
DO - 10.1016/S0020-1693(02)01516-5
M3 - Article
AN - SCOPUS:0142184861
VL - 350
SP - 299
EP - 313
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
SN - 0020-1693
ER -