Abstract
AbstractReactions 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.
Published Version
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