Substitution and Catalytic Chemistry of Gyroscope‐Like Complexes Derived from Cl–Rh–CO Rotators and Triply trans Spanning Di(trialkylphosphine) Ligands Academic Article uri icon

abstract

  • © 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Reactions of trans-[Rh(CO)(Cl){P{(CH2)14}3P2(Rh-P2)}] (1) with ZnPh2, MeLi, or NaBH4 give the chloride-substitution products trans-[Rh(CO)(Ph){P{(CH2)14}3P2(Rh-P2)}] (3, 89 %), trans-[Rh(CO)(Me){P{(CH2)14}3P2(Rh-P2)}] (94 %, 92 % purity), and trans-[Rh(CO)(H2BH2){P{(CH2)14}3P2(Rh-P2)}] (5, 99 %). The crystal structures of 3, 5, and the corresponding (fortuitously obtained) bromide complex are determined, and the ability of the X-Rh-CO moieties to rotate is interpreted in terms of their effective radii and the void space within the dibridgehead diphosphine cage. Reaction of 1 and excess PMe3 gives the diphosphine substitution product trans-[Rh(CO)(Cl)(PMe3)2] (89 %) and the dibridgehead diphosphine P[(CH2)14]3P (58 %). Complex 5 serves as a catalyst precursor for the hydroformylation of 1-octene (neat or THF, 60 °C, 75 psig 1:1 CO/H2). The locus of catalysis with respect to the diphosphine cage is discussed.

altmetric score

  • 0.25

author list (cited authors)

  • Estrada, A. L., Jia, T., Bhuvanesh, N., Blümel, J., & Gladysz, J. A.

citation count

  • 15

publication date

  • October 2015

publisher