Copper(I) Complexes of Amide Functionalized Bisphosphine: Proximity Enhanced Metal–Ligand Cooperativity and Its Catalytic Advantage in C(sp3)–H Bond Activation of Unactivated Cycloalkanes in Dehydrogenative Carboxylation Reactions

The reactions of amide functionalized bisphosphine, o-Ph2PC6H4C-(O)N(H)C6H4PPh2-o (1) (BalaHariPhos), with copper salts is described. Treatment of 1 with CuX in a 1:1 molar ratio yielded chelate complexes of the type [CuX{(o-Ph2PC6H4C(O)N(H)C6H4PPh2-o)}-κ2-P,P] (X = Cl, 2; Br, 3; and I, 4), which on subsequent treatment with KOtBu resulted in a dimeric complex [Cu(o-Ph2PC6H4C(O)(N)C6H4PPh2-o)]2 (5). Interestingly, complexes 2–4 showed weak N–H···Cu interactions. These weak H-bonding interactions are studied in detail both experimentally and computationally. Also, CuI complexes 2–5 were employed in the oxidative dehydrogenative carboxylation (ODC) of unactivated cycloalkanes in the presence of carboxylic acids to form the corresponding allylic esters. Among complexes 2–5, halide-free dimeric CuI complex 5 showed excellent metal–ligand cooperativity in the oxidative dehydrogenative carboxylation (ODC) in the presence of carboxylic acids to form the corresponding allylic esters through C(sp3)–H bond activation of unactivated cycloalkanes. Mechanistic details of the catalytic process were established by isolating the precatalyst [Cu{(o-Ph2PC6H4C(O)(NH)C6H4PPh2-o)-κ2-P,P}(OOCPh)] (6) and fully characterized by mass spectrometry, NMR data, and single-crystal X-ray analysis. Density functional theory-based calculations further provided a quantitative understanding of the energetics of a series of H atom transfer steps occurring in the catalytic cycle.