Übergangsmetall-substituierte Phosphane, Arsane und Stibane, XXX Redoxreaktionen zwischen Triorganodibromphosphoranen oder -arsoranen und Ubergangsmetall -Anionen / Transition-Metal Substituted Phosphanes, Arsanes and Stibanes, XXX Redox Reactions between Triorganodibromophosphoranes or -arsoranes and Transition Metal Anions

Abstract

Abstract The reaction of the sodium carbonyl metalate Na[W(CO)3Cp] with the phosphorane (Me3SiCH2)3PBr2 results in the formation of (Me3SiCH2)3PandCp(CO)3WBr or [Cp(CO)3W]2, respectively, depending on the solvent used. The redox reactions between Na[Mo(CO)3Cp] and the arsenic analogue (RCH2)3AsBr2 (R = Ph, Me3Si) yield the products Cp(CO)sMoBr 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)2[As(CH2R)3]MBr (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)2[E(CH2R)3]MBr (2c, 3). The dynamic behaviour of the chiral complexes 1, 2a, b, was investigated by 1H NMR spectroscopy.