160260-61-7Relevant academic research and scientific papers
Reaction of (1-) with the (1+) Cation involving Insertion of an Os(CO)4 Fragment into the Gold-Phosphorus Bond
Cathey, Christopher,Lewis, Jack,Raithby, Paul R.,Ramirez de Arellano, M. Carmen
, p. 3331 - 3332 (1994)
The reaction of the cluster anion (1-) 1 with (1+) affords the cluster (μ-Cl)(CO)10> 2 which represents the first example in which an Os(CO)4 fragment has been inserted in to a gold-phosphine bond; the structure of 2 has been established by a single-crystal X-ray analysis.
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
Al-Mandhary, Muna R.A.,Buntem, Radchada,Cathey, Christopher,Lewis, Jack,De Arellano, M. Carmen Ramirez,Shields, Gregory P.,Doherty, Cheryl L.,Raithby, Paul R.
, p. 299 - 313 (2008/10/08)
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.
