220821-76-1Relevant articles and documents
Phosphenium complexes 30. Supermesitylphosphenium complexes of molybdenum and tungsten: Synthesis and exchange reactions involving the P-H bond
Malisch, Wolfgang,Hirth, Ulrich-Andreas,Gruen, Klaus,Schmeusser, Martin
, p. 207 - 212 (2007/10/03)
Deprotonation of the complex salts {Cp(OC)3[H2(2,4,6-tBu3-C6H 2)P]M}BF4 (M=Mo, W) (4a,b), obtained from [Cp(OC)3M]BF4 (2a,b) and (2,4,6-tBu3-C6H2)PH2 (3), yields the metallo-phosphanes Cp(OC)3M-P(H)(2,4,6-tBu3-C6H2) (5a,b). 5a,b are thermally decarbonylated to the PH-functionalized phosphenium complexes Cp(OC)2M=P(H)(2,4,6-tBu3-C6H2) (7a,b), which can also be obtained by the base-assisted dehydrohalogenation of the bifunctional complexes Cp(OC)2[H2(2,4,6-tBu3C6H 2)P]M-Cl (9a,b), prepared by a ligand exchange reaction from Cp(OC)3M-Cl (8a,b) and 3. The reaction of 7a,b with CCl4 affords the chloro-substituted phosphenium complex Cp(OC)2M=P(Cl)(2,4,6-tBu3-C6H2) (10a,b) via H/Cl exchange at the sp2-phosphorus. Substitution of the P-bonded hydrogen by a methyl group is achieved by in situ deprotonation of 7b and subsequent treatment with methyliodide, yielding the diorgano-phosphenium complex Cp(OC)2M=P(Me)(2,4,6-tBu3-C6H2) (11).