Metal hydrides form halogen bonds: Measurement of energetics of binding

TY - JOUR

T1 - Metal hydrides form halogen bonds

T2 - Measurement of energetics of binding

AU - Smith, Dan A.

AU - Brammer, Lee

AU - Hunter, Christopher A.

AU - Perutz, Robin N.

PY - 2014/1/29

Y1 - 2014/1/29

N2 - The formation of halogen bonds from iodopentafluorobenzene and 1-iodoperfluorohexane to a series of bis(η-cyclopentadienyl) metal hydrides (CpTaH, 1; CpMH, M = Mo, 2, M = W, 3; CpReH, 4; CpTa(H)CO, 5; Cp = η-cyclopentadienyl) is demonstrated by H NMR spectroscopy. Interaction enthalpies and entropies for complex 1 with C FI and CFI are reported (ΔH = -10.9 ± 0.4 and -11.8 ± 0.3 kJ/mol; ΔS = -38 ± 2 and -34 ± 2 J/(mol·K), respectively) and found to be stronger than those for 1 with the hydrogen-bond donor indole (ΔH = -7.3 ± 0.1 kJ/mol, ΔS = -24 ± 1 J/(mol·K)). For the more reactive complexes 2-5, measurements are limited to determination of their low-temperature (212 K) association constants with CFI as 2.9 ± 0.2, 2.5 ± 0.1,

AB - The formation of halogen bonds from iodopentafluorobenzene and 1-iodoperfluorohexane to a series of bis(η-cyclopentadienyl) metal hydrides (CpTaH, 1; CpMH, M = Mo, 2, M = W, 3; CpReH, 4; CpTa(H)CO, 5; Cp = η-cyclopentadienyl) is demonstrated by H NMR spectroscopy. Interaction enthalpies and entropies for complex 1 with C FI and CFI are reported (ΔH = -10.9 ± 0.4 and -11.8 ± 0.3 kJ/mol; ΔS = -38 ± 2 and -34 ± 2 J/(mol·K), respectively) and found to be stronger than those for 1 with the hydrogen-bond donor indole (ΔH = -7.3 ± 0.1 kJ/mol, ΔS = -24 ± 1 J/(mol·K)). For the more reactive complexes 2-5, measurements are limited to determination of their low-temperature (212 K) association constants with CFI as 2.9 ± 0.2, 2.5 ± 0.1,

UR - http://www.scopus.com/inward/record.url?scp=84893444143&partnerID=8YFLogxK

U2 - 10.1021/ja4121499

DO - 10.1021/ja4121499

M3 - Article

AN - SCOPUS:84893444143

SN - 0002-7863

VL - 136

SP - 1288

EP - 1291

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 4

ER -