期刊
JOURNAL OF ORGANOMETALLIC CHEMISTRY
卷 865, 期 -, 页码 114-127出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2018.02.014
关键词
B-H center dot center dot center dot pi H-Bond; Synthesis of Ir-Phosphine complexes; Borane-benzene complexes; Local stretching force constants; Bond strength orders; Energy density H(r)
资金
- National Science Foundation [CHE 1152357, CHE 1464906]
- National Natural Science Foundation [21472086, 21531004]
Boranes and carboranes form non-classical H-bonds with the p-face of an arene provided entropic factors are excluded, for example via a suitably designed template. The self-assembled Ir-dithiolene phosphine complexes of the type [Cp*Ir(PR3)S2C2B10H10] (R = C6H4X, X = H, F, OMe) provide such a template. Steric crowding causes that one of the B-H bonds of the carborane is positioned above the phenyl plane of R to form a non-classical B-H center dot center dot center dot pi hydrogen bond. For the gas phase, this is predicted by quantum chemical calculations of the local B-H center dot center dot center dot pi stretching force constants. The solid-state structures of six [Cp*Ir(PR3)S2C2B10H10] complexes synthesized are in close agreement with the quantum chemical predictions thus suggesting the existence of B-H center dot center dot center dot pi hydrogen bonds. The H-1[B-11] NMR titration experiments reveal that non-covalent B-H center dot center dot center dot pi bonds also exists in solution. Calculations show that the bond strength order of the B-H center dot center dot center dot pi H-bond determined with the help of the local stretching force constant is 0.35, comparable to what is found for the H-bond in the water dimer. However, the B-H center dot center dot center dot pi H-bond is electrostatic in nature as confirmed by the topological analysis of the electron density rho(r). The role of this H-bond in carborane supramolecular chemistry is elucidated and discussed. (C) 2018 Published by Elsevier B.V.
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