1079247-16-7Relevant academic research and scientific papers
Dinuclear (arene)ruthenium complexes containing a chiral-at-phosphorus phosphanido bridge
Tschan, Mathieu J.-L.,Suess-Fink, Georg,Cherioux, Frederic,Therrien, Bruno
, p. 3091 - 3100 (2007)
The unsaturated diruthenium cation [(η6-C6Me 6)(η6-p-iPrMeC6H4)Ru 2(μ2-H)3]+ reacts with PPh 2(CH2)3Ph to give the phosphanido complex [(η6-C6Me6)(η6-p-iPrMeC 6H4)-Ru2{μ2-PPh(CH 2)3Ph}(μ2-H)2]+ (1), which contains a stereogenic phosphorus atom in the bridge, and benzene. Heating of 1 in bromobenzene gives the first chiral-at-phosphorus diruthenium complex [(η6-C6Me6)Ru2{μ2- PPh(CH2)3-η6-Ph}(μ2-Br) 2]+ (3) due to the replacement of the p-cymene ligand by the phenyl group at the pendant arm and hydrido bridges by bromido bridges. The single-crystal X-ray structure analysis of [3][BF4] reveals a racemic mixture of both enantiomers (RP)-3 and (SP)-3 in the crystal. Similarly, the reaction of [(η6-C6Me 6)(η6-p-iPrMeC6H4)Ru 2(μ2-H)3]+ and the enantiopure phosphane (R)-PPh2(CH2)2CHMePh yields the complex [(η6-C6Me6)(η6-p- iPrMeC6H4)Ru2{μ2-(R)-PPh(CH 2)2CHMePh}(μ2-H)2]+ (4) as a mixture of diastereomers. An optically active mixture (de = 4 %) of phosphanido-bridged complexes [(η6-C6Me 6)Ru2{μ2-(R)-PPh(CH2) 2CHMe-η6-Ph}(μ2-Br)2] + (6), containing the (RC,SP) and (R C,RP) diastereomers, is obtained upon heating of 4 in bromobenzene. The molecular structure of [6][BF4] reveals that the two diastereomers (RC,SP)-6 and (RC,R P)-6 exist as two conformers. The non-chiral-at-phosphorus analogues [(η6-C6Me6)2Ru 2[μ2-PPh(CH2)3Ph] (μ2-H)2]+ (2) and [(η6-C 6Me6)2Ru2{μ2-(R) -PPh(CH2)2CHMePh}(μ2-H)2] + (5) have also been synthesized and structurally characterized by single-crystal X-ray structure analyses of [2][BF4] and [5][BF 4]. Wiley-VCH Verlag GmbH & Co. KGaA.
