Organometallics p. 3064 - 3068 (1993)
Update date:2022-08-04
Topics:
Pedersen, Astrid
Tilset, Mats
In acetonitrile solution, Cpz.ast;Ir(PPh3)(H)3+BF4- smoothly undergoes elimination of pentamethylcyclopentadiene (Cp*H) to yield Ir(H)2(PPh3)(NCMe)3+BF 4- as the only Ir-containing product (δH? = 69.0 ± 2.1 kJ/mol, ΔS? = -82.0 ± 7.6 J/(K·mol), k(20°C) = 1.6 × 10-4 s-1). The elimination of Cp*H did not take place in neat dichloromethane. The rate law exhibited a mixed first- and second-order dependence on the acetonitrile concentration, in accord with a mechanism involving successive acetonitrile-mediated η5 to η3 to η1 ring slippage reactions, the first of which is reversible.
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(1993)
