Abstract
The interactions of Pt and Pd acyl complexes with Lewis acids are investigated through experiment and computation. Variable-temperature NMR studies indicate BF3 association with trans-[(PPh3)2(CO)Pt(COCH2Ph)][BArF4] (3; BArF4 = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) at 298 K is endergonic (ΔG° = 2.0 kcal mol–1) yet exothermic (ΔH° = −3.4 kcal mol–1), suggesting a Lewis basicity comparable to or greater than aldehydes and ketones. Despite the accelerating effect of Lewis acids in the formation of the Pd congener trans-[(PPh3)2(CO)Pd(COCH2Ph)][BArF4] (4), no evidence for adduct formation was obtained. DFT (M06-L/def2-TZVP/QZVP) suggests that BF3/trans-[(PPh3)2(CO)M(COCH2Ph)]+ adduct formation is more favored for M = Pt than M = Pd. Natural bond orbital analysis shows that upon Lewis acid coordination, the acyl C–O bond is weakened, the natural charge of the acyl C is more positive, and the π*acyl C–O orbital is lowered in energy relative to other unoccupied orbitals.
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