A cationic Rh(III) complex that efficiently catalyzes hydrogen isotope exchange in hydrosilanes.
The synthesis and structural characterization of a mixed-sandwich (η(5)-C(5)Me(5))Rh(III) complex of the cyclometalated phosphine PMeXyl(2) (Xyl = 2,6-C(6)H(3)Me(2)) with unusual κ(4)-P,C,C',C'' coordination (compound 1-BAr(f); BAr(f) = B(3,5-C(6)H(3)(CF(3))(2))(4)) are reported. A reversible κ(4) to κ(2) change in the binding of the chelating phosphine in cation 1(+) induced by dihydrogen and hydrosilanes triggers a highly efficient Si-H/Si-D (or Si-T) exchange applicable to a wide range of hydrosilanes. Catalysis can be carried out in an organic solvent solution or without solvent, with catalyst loadings as low as 0.001 mol %, and the catalyst may be recycled a number of times.
Departamento de Química Inorgánica-Instituto de Investigaciones Químicas, Universidad de Sevilla-Consejo Superior de Investigaciones Científicas, Avda. Américo Vespucio 49, Isla de la Cartuja, 41092 Sevilla, Spain.
Jesús
J
Campos
Ana C
AC
Esqueda
Joaquín
J
López-Serrano
Luis
L
Sánchez
Fernando P
FP
Cossio
Abel
A
de Cozar
Eleuterio
E
Alvarez
Celia
C
Maya
Ernesto
E
Carmona
D002384:Catalysis; D003903:Deuterium / Q000737:chemistry*; D041961:Deuterium Exchange Measurement; D009942:Organometallic Compounds / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D012821:Silanes / Q000737:chemistry*; D014316:Tritium / Q000737:chemistry*
D009942:Organometallic Compounds; D012821:Silanes; D014316:Tritium; D003903:Deuterium; D012238:Rhodium