Two pathways of proton transfer reaction to (triphos)Cu(η1-BH4) via a dihydrogen bond [triphos = 1, 1, 1-tris(diphenylphosphinomethyl)ethane]. Issue 22 (10th May 2016) - Golub, I. E.
Abstract : The interaction of alcohols of variable strength with the copper(i ) borohydride complex (triphos)Cu(η 1 -BH4 ) results in a great variety of DHB complexes which encompass different mechanisms involving M–H and E–H bond (E = B, O) activation steps. Abstract : The interaction of the η 1 -tetrahydroborate copper(i ) complex (triphos)Cu(η 1 -BH4 ) (1 ) with proton donors [CF3 CH2 OH (TFE), (CF3 )2 CHOH (HFIP), (CF3 )3 COH (PFTB), PhOH, p -NO2 C6 H4 OH (PNP), p -NO2 C6 H4 NNC6 H4 OH (PNAP), CF3 OH] was a subject of a combined IR spectroscopic and theoretical investigation. Spectral (Δ ν ) and thermodynamic (Δ H ) parameters of dihydrogen bond (DHB) formation were determined experimentally. The terminal hydride ligand (characterized by the basicity factor E j (BH) = 0.87 ± 0.01) is found to be a site of proton transfer which begins with nucleophilic substitution of BH4 − by the alcohol oxygen atom on the copper center ( BH pathway ). The activation barrier computed for (CF3 )2 CHOH in CH2 Cl2 – Δ G ‡273 K = 20.6 kcal mol −1 – is in good agreement with the experimental value (Δ G ‡270 K = 20.0 kcal mol −1 ). An abnormal dependence of the reaction rate on the proton donor strength found experimentally in dichloromethane is explained computationally on the basis of the variation of the structural and energetic details of this process with the proton donor strength. In the second reaction mechanism found ( CuH pathway ), DHB complexes with the initial ROH coordination to the bridging hydride lead to B–Hbr bond cleavage with BH3 elimination. "Copper assistance" via the Cu⋯O interaction is not involved. This mechanism can be evoked to explain the occurrence of proton transfer in coordinating solvents.