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B–H···π Interaction: A New Type of Nonclassical Hydrogen Bonding

Xiaolei ZhangState Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu 210093, ChinaHuimin DaiState Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu 210093, ChinaHong YanState Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu 210093, ChinaWenli ZouComputational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University, Dallas, Texas 75275-0314, United StatesDieter CremerComputational and Theoretical Chemistry Group (CATCO), Department of Chemistry, Southern Methodist University, Dallas, Texas 75275-0314, United States

2016en

ABI

Annotatsiya

For the first time, nonclassical hydrogen (H)-bonding involving a B-H···π interaction is described utilizing both quantum chemical predictions and experimental realization. In the gas phase, a B-H···π H-bond is observed in either B2H6···benzene (ΔE = -5.07 kcal/mol) or carborane···benzene (ΔE = -3.94 kcal/mol) complex at reduced temperatures. Ir-dimercapto-carborane complexes [Cp*Ir(S2C2B10H10)] are designed to react with phosphines PR3 (R = C6H4X, X = H, F, OMe) to give [Cp*Ir(PR3)S2C2B10H10] for an investigation of B-H···π interactions at ambient temperatures. X-ray diffraction studies reveal that the interaction between the carborane BH bonds and the phosphine aryl substituents involves a BH···π H-bond (H···π distance: 2.40-2.76 Å). (1)H NMR experiments reveal that B-H···π interactions exist in solution according to measured (1)H{(11)B} signals at ambient temperatures in the range 0.0 ≤ δ ≤ 0.3 ppm. These are high-field shifted by more than 1.5 ppm relative to the (1)H{(11)B} signals obtained for the PMe3 analog without B-H···π bonding. Quantum chemical calculations suggest that the interaction is electrostatic and the local (B)H···ring stretching force constant is as large as the H-bond stretching force constant in the water dimer.

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DOI: 10.1021/jacs.6b01249

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