The complex (5,10,15,20-tetraphenylporphinato)bis(tri-n-butylphosphine)iron(II), 1, has been isolated in a triclinic crysgl form, a = 12.499(3), b = 12.528(2), c = 12.039(2) A, u = 116.39(1), P = 109.79(1), y = 98.13(1)", Z = 1, spacegroup P1.The structure was solved by conventional heavy atom methods and was refined by full-matrix least-squares procedures to R = 0.060 and R,, = 0.070 for 3551 reflections with I ? 3 u(l). The molecule, which has crystallographic 1-Ci symmetry, displays a relatively undistorted pseudo-octahedral coordination geometry with Fe-P = 2.346(1) and Fe-N = 1.998(3) and 1.993(3) A.In CH2C1, solution, 1 reacts with CO and aldehydes to generate the carbonyl(phosphine) derivative, and decarbonylation of phenylacetaldehyde to toluene becomes catalytic under an Ar stream. The aldehyde decarbonylations involve radical pathways via carbonyl loss from PhCH2C0. The hydrogen abstraction/initiation reaction probably utilizes trace O2 (and possibly trace (water); speculative mechanisms are discussed. [Traduit par la revue] Introduction Carbonylation reactions provide key steps in a range of homogeneously catalyzed processes of industrial importance (1, 2). Decarbonylation (for example, of aldehydes: RCHO +
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