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Issue 22, 2016
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Two pathways of proton transfer reaction to (triphos)Cu(η1-BH4) via a dihydrogen bond [triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane]

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Abstract

The interaction of the η1-tetrahydroborate copper(I) complex (triphos)Cu(η1-BH4) (1) with proton donors [CF3CH2OH (TFE), (CF3)2CHOH (HFIP), (CF3)3COH (PFTB), PhOH, p-NO2C6H4OH (PNP), p-NO2C6H4N[double bond, length as m-dash]NC6H4OH (PNAP), CF3OH] was a subject of a combined IR spectroscopic and theoretical investigation. Spectral (Δν) and thermodynamic (ΔH) parameters of dihydrogen bond (DHB) formation were determined experimentally. The terminal hydride ligand (characterized by the basicity factor Ej(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)2CHOH in CH2Cl2 – ΔG273 K = 20.6 kcal mol−1 – is in good agreement with the experimental value (ΔG270 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.

Graphical abstract: Two pathways of proton transfer reaction to (triphos)Cu(η1-BH4) via a dihydrogen bond [triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane]

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Supplementary files

Article information


Submitted
21 Mar 2016
Accepted
21 Apr 2016
First published
10 May 2016

This article is Open Access

Dalton Trans., 2016,45, 9127-9135
Article type
Paper

Two pathways of proton transfer reaction to (triphos)Cu(η1-BH4) via a dihydrogen bond [triphos = 1,1,1-tris(diphenylphosphinomethyl)ethane]

I. E. Golub, O. A. Filippov, N. V. Belkova, L. M. Epstein, A. Rossin, M. Peruzzini and E. S. Shubina, Dalton Trans., 2016, 45, 9127
DOI: 10.1039/C6DT01104G

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