Reactions of coordinated ligands. VIII. Synthesis and characterization of molybdenum carbonyl complexes of diphenylphosphinous acid and diphenylphosphinous acid derivatives

Academic Article


  • Several unexpected reactions have led to syntheses of cis-[Mo(CO)4((PPh2)2-E)] in which E = O, S, NH. The E = O complex was obtained from the reactions of several acid chlorides (CH3C(O)Cl, PCl3, (MeO)P(O)Cl2 and [Mo(CO)5-(PMe2Cl)]) with [Et3NH]+ cis-[Mo(CO)4((PPh2O)2H)]-. The E = NH analog arose from the reaction of BF3 · O(C2H5)2 with cis-[Mo(CO)4(PPh2NH2)2] and the E = S complex resulted from the reaction of H2S with cis-[Mo(CO)4(PPh2-Cl)2]. The unsymmetrically substituted complex cis-[Mo(CO)4(PPh2OH)-(PPh2OCH2CH3)] was obtained from the reaction of cis-[Mo(CO)4(PPh2Cl)2] with excess sodium ethoxide in ethanol. Cleavage of a PS bond in cis-[Mo-(CO)4((PPh2)2S] with NaOH in the presence of Et4N+Cl- yielded the unsymmetrical complex [Et4N]+ cis-[Mo(CO)4((PPh2O)(PPh2S)H)]-. Synthesis of cis-[Mo(CO)4((PPh2O)2P(O)CH2Cl)] was accomplished by reacting (ClCH2)-P(O)(OH)2 with cis-[Mo(CO)4(PPh2Cl)2]. Multinuclear NMR (1H, 13C, 17O, 31P) and IR spectroscopy assisted in complex characterization. Conductance measurements on acetone solutions proved the complexes [Et3NH]+ cis-[Mo(CO)4-((PPh2O)2E)]-, where E = H+, BF2+, and [Et4N]+ cis-[Mo(CO)4((PPh2O)-(PPh2Y)H)]-, where Y = O, S, to be 1/1 electrolytes. © 1982.
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  • Gray GM; Kraihanzel CS
  • Start Page

  • 209
  • End Page

  • 222
  • Volume

  • 238
  • Issue

  • 2