Shiu Kom-Bei, Peng Shie-Ming, M. Cheng
Nov 30, 1993
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0
Influential Citations
6
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Journal
Journal of Organometallic Chemistry
Abstract
Abstract Reaction of [MO(pip) 2 (CO) 4 ] (pip=piperidine) with (S, S) − in acetonitrile gives readily [Moη 2 -(S, S)(CO) 4 ] − , isolated as [PPN][Mo(η 2 -(S, S))(CO) 4 ] (PPN + = bis(triphenylphosphine)iminium; (S, S) − = pyrrolidine- ( 1 ) or piperidine-1-carbodithioato ( 2 )). The two compounds have been characterized by elemental analysis, IR, nuclear magnetic resonance and X-ray crystallography. 1 : monoclinic, P 2 1 / n ; a = 16.207(5), b = 12.804(3) A, c = 20.398(4) A; β = 91.02(2)°; V = 4232(2) A 3 , Z = 4; R = 0.034, R w = 0.037 based on 4989 reflections with I > 3.0σ( I ). 2 : monoclinic, P 2 1 / n ; a = 14.148(4) A, b = 13.646(5) A, c = 22.535(8) A; β = 95.92(3)°; V = 4327(3) A 3 , Z = 4; R = 0.054, R w = 0.041 based on 2048 reflections with I > 2.0σ( I ). No appreciably modified ligand structure is found in response to the different p K a of the amine used to form the specific (S, S) − in the compounds. This feature is rationalized by the electron-withdrawing effect of the metal carbonyl fragment, leading to the observed similarity in both the CO stretching and the MoCO distances.