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Transition-Metal Substituted Phosphanes, Arsanes and Stibanes, XXX. Redox Reactions between Triorganodibromophosphoranes or -arsoranes and Transition Metal Anions
Meyer, Angelika,Hartl, Anna,Malisch, Wolfgang
, p. 845 - 850 (2007/10/02)
The reaction of the sodium carbonyl metalate Na with the phosphorane (Me3SiCH2)3PBr2 results in the formation of (Me3SiCH2)3P and Cp(CO)3WBr or 2 respectively, depending on the solvent used.The redox reactions between Na and the arsenic analogue (RCH2)3AsBr2 (R = Ph, Me3Si) yield the products Cp(CO)3MoBr and (RCH2)3As.A mechanism involving radicals is discussed.At elevated temperatures the products react further to give the square pyramidal complexes cis-Cp(CO)2MBr (1,2a,b) with loss of CO.In an analogous manner Cp(CO)3MBr (M = Mo, W) and (RCH2)3E (E = As, Sb) afford compounds cis-Cp(CO)2MBr (2c, 3).The dynamic behaviour of the chiral complexes 1, 2a, b, was investigated by 1H NMR spectroscopy. - Key words: Transition Metal Nucleophiles, Redox Reaction, Stereospecific CO-Substitution, Dynamic Behaviour
