Please use this identifier to cite or link to this item: https://doi.org/10.1021/ic025589c
Title: 1,2,3,4-Tetraphenyl-1,2,3,4-tetraphospholane, a highly versatile cyclocarbaphosphine ligand: Reactions with activated triosmium clusters and characterization of the products
Authors: Ang, S.-G. 
Zhong, X. 
Ang, H.-G. 
Issue Date: 15-Jul-2002
Citation: Ang, S.-G., Zhong, X., Ang, H.-G. (2002-07-15). 1,2,3,4-Tetraphenyl-1,2,3,4-tetraphospholane, a highly versatile cyclocarbaphosphine ligand: Reactions with activated triosmium clusters and characterization of the products. Inorganic Chemistry 41 (14) : 3791-3800. ScholarBank@NUS Repository. https://doi.org/10.1021/ic025589c
Abstract: Reaction of 1,2,3,4-tetraphenyl-1,2,3,4-tetraphospholane (I) with [Os3(CO)11(NCMe)] at ambient temperature affords substituted clusters: the monosubstituted trinuclear cluster [Os3(CO)11{(PPh)4CH2}] (1) and the isomeric linked bis-trinuclear clusters [{Os3(CO)11}2{μ-1,4-η2 -(PPh)4CH2}] (2) and [{Os3(CO)11}2{μ-1,3-η2- (PPh)4CH2}] (3). Clusters 2 and 3 can also be prepared by further reaction of 1 with [Os3(CO)11(NCMe)]. The reaction at 100 °C gives, apart from cluster 2, the disubstituted 1,4-bridged trinuclear cluster [Os3(CO)10{μ-1,4-η2 -(PPh)4CH2}] (4). The conversion of 1 into 4 can be achieved through the pyrolysis of a solution of 1. When 1 reacts with an equimolar amount of [Os3(CO)10(μ-H)2] at 100 °C in toluene, the 1,2,4-linked bis-trinuclear cluster [Os3(CO)11{μ3-1,2,4-η3 -(PPh)4CH2}-Os3(CO)8 (μ-H)2] (5) is obtained. When I reacts with a 2-fold molar amount of [Os3(CO)10(μ-H)2], the 1,2,3,4-linked bis-trinuclear hydride cluster [{Os3(CO)8(μ-H)2}2 {μ4-1,2,3,4-η4-(PPh)4CH2}] (6) is obtained. Cluster 1 exists as two conformational isomers (1y and 1r) in the crystalline state, due to different conformational arrangements of pseudoaxial carbonyls in the cluster. Cluster 3 shows two interconvertible conformers (3y and 3r) due to the inversion of the configuration of the uncoordinated outer phosphorus atom, and a pair of enantiomers exists in 3r. All of the new compounds obtained have been characterized by spectroscopic and analytical techniques, and their structures have been established by X-ray crystallography.
Source Title: Inorganic Chemistry
URI: http://scholarbank.nus.edu.sg/handle/10635/92894
ISSN: 00201669
DOI: 10.1021/ic025589c
Appears in Collections:Staff Publications

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