Journal
ORGANOMETALLICS
Volume 30, Issue 15, Pages 4039-4051Publisher
AMER CHEMICAL SOC
DOI: 10.1021/om200288e
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The reaction of [Rh(coe)(2)Cl](2) with the ligands P(Pr-i)(2)-O-Ph-pX-CO-Ph-pX-O-P(Pr-i)(2) (L1 X = H and L2 X = OMe) containing a benzophenone moiety resulted in the quantitative oxidative addition of the PhC-CO single bond under very mild conditions (193 K, 2a/b). For L2 the mechanism and the kinetics of the oxidative addition were investigated. Only complex 2a (X-ray crystal structure included) shows an exchange of the metal-bonded carbon moieties via migratory extrusion/insertion (3a) in solution. Thermodynamic parameters for this process were determined (for 3a -> 2a Delta H degrees = 9.3 +/- 0.5 kJ/mol, Delta S degrees = 53.8 +/- 1.8 J/(K mol)). The further fate, in particular the reductive elimination, of 2a/b was investigated and compared to the behavior of Ir. The reaction of 2a/b with several Lewis bases such as CO, (CO)-C-13, tert-butyl isonitrile, pyridine, acetonitrile, and N-15-acetonitrile was investigated. DFT calculations for the most important steps were performed.
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