Synthesis, structures and ligating properties of 2,6-bis(phosphino) thiophenol derivatives

摘要

New t-butyl-aryl thioethers where the aryl group is 2,6-bis(phosphino) phenyl have been synthesized. The syntheses were completed via sequential ortho-lithiations of t-butylphenylsulfide, followed by chlorophosphine (ClPR2) quenches; symmetric (2,6-bis(diphenylphosphino) phenyl, (4a)) and unsymmetric (2-diisopropylphosphino-6-diphenylphosphino) phenyl, (4b) aryl groups were obtained. Treatment of 4a with Li or Na naphthalenide yielded 2,6-bis(diphenylphosphino) thiophenol 5. Reactions of 4a or 5 with NiCl2 center dot 6H(2)O yielded nickel bis(phosphinothiophenolate) 6. Compounds 4a, b, 5 and 6 were characterized by H-1 and P-31 NMR, and by mass-spectrometry. In addition, 4a, 5 and 6 were characterized by single crystal X-ray diffraction methods. (C) 2007 Elsevier B.V. All rights reserved.