Journal of the Chemical Society, Dalton Transactions p. 1963 - 1970 (1994)
Update date:2022-07-31
Topics:
Gash, Rosslyn C.
Cole-Hamilton, David J.
Whyman, Robin
Barnes, John C.
Simpson, Michael C.
Diiodomethane oxidatively added to a mixture of bromo- and chloromethyl complexes whilst CH2ICl gave two isomers of a halide-scrambling reaction to give several compounds containing CH2I or CH2Cl ligands which have been identified spectroscopically.The same scrambling occurs under high pressures of CO, although IR, NMR and model studies suggest the Rh-C(O)CH2X species are also formed by insertion of CO into the Rh-CH2X bond.Most of the acyl products are unstable to loss of ketene, but one may be stable <ν(C=O) 1665 cm-1>.The complex a=12.343(3), b=14.327(2), c=15.426(2) Angstroem, α=113.78(1), β=67.25(1), γ=90.20(1) deg, Z=4, R=0.0453.Each unit cell contains two pairs of molecules differing in the relative orientations of one PEt3 ligand.In both cases, Rh-C <2.080(6), 2.063(9) Angstroem>, C-I <2.151(9), 2.121(10( Angstroem> and Rh-C-I <119.9(5), 120.3(4) deg> are similar to those reported for related compounds.Both molecules have mutually trans phosphines and CH2I trans to I.
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