6533b85cfe1ef96bd12bd1d4

RESEARCH PRODUCT

Photochemical ligand rearrangement in dirhodium(II) compounds. Structure of Rh2(O2CCH3)2(η2-O2CCH3)[(C6H4)PPh2] (η2-PCCl)(PCClP-ClC6H4)Ph2

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Abstract The photochemical reaction of the adducts Rh2(O2CCH3)3[(C6H4)P(o-ClC6H4)Ph]· (P(p-XC6H4)3) (X=H, Me, Cl), yield the compounds Rh2(O2CCH3)2(η2-O2CCH3)[(p-XC6H3)P (p-XC6H4)2](η2-PCCl), (PCCl=P(o-ClC6H4)Ph2) in a ligand rearrangement reaction that involves activation of CH and RhC bonds. The factors that favour this process are studied by carrying out photochemical reactions with different phosphines. The structures of Rh2(O2CCH3)2(η2-O2CCH3) [(C6H4)PPh2](η2-PCCl) has been determined by X-ray diffraction. Mr=1321.1, orthorhombic, space group Pbcn, a=20.339(8), b=20.07(6), c=23.07(3) A , V=9413(3) A 3 , Z=8, D x =1.86 g cm −3 . Mo Kα radiation (graphite crystal monochromator, λ=0.071073 A ), μ(Mo Kα) = 13.83 cm−1, F(000)=5280, T=293 K. Final conventional R factor=0.062 for 4889 ‘observed’ reflections and 500 variables. The compound contains three bridging ligands, two acetates and one metalated triphenylphosphine, and two chelating ligands, one acetate and one PCCl that acts as a P,Cl ligand, taking one equatorial (P) and one axial (Cl) coordination site. The axial RhCl bond distance is 2.573(4) A.