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
2014
Meyer, Angelika | Hartl, Anna | Malisch, Wolfgang
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.
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