Spectroscopic Evidence for Intermolecular M−H···H−OR Hydrogen Bonding: Interaction of WH(CO)2(NO)L2 Hydrides with Acidic Alcohols
Elena S. Shubina
1
,
Aleksandr N Krylov
1
,
Evgeni V Vorontsov
1
,
Lina M. epstein
1
,
Dmitri G Gusev
1
,
Martina Niedermann
1
,
Heinz Berke
1
Publication type: Journal Article
Publication date: 1996-01-01
scimago Q1
wos Q1
SJR: 5.554
CiteScore: 22.5
Impact factor: 15.6
ISSN: 00027863, 15205126
General Chemistry
Catalysis
Biochemistry
Colloid and Surface Chemistry
Abstract
Intermolecular hydrogen bonding of acidic alcohols (PhOH, (CF3)2CHOH (HFIP), (CF3)3CHOH (PFTB)) to the hydride ligand of WH(CO)2(NO)L2 (L = PMe3 (1), PEt3 (2), P(OiPr)3 (3), PPh3 (4)) has been observed and characterized by IR and NMR spectroscopy in hexane, toluene-d8, and CD2Cl2 solutions. The H-bonding is an equilibrium process with medium −ΔH° of 4.1−6.9 kcal/mol; the enthalpy increases on going from 4 to 1, i.e., the strongest bonding is found for the smallest and the most basic L = PMe3. The value of −ΔH° depends on the pKa of the proton donors, increasing as the acidity does (PhOH < HFIP < PFTB). The IR and NMR data suggest C2v symmetry around tungsten in the ROH···HW(CO)2(NO)L2 adduct, with the H···H distance of 1.77 A (L = PMe3) estimated from the hydride T1min relaxation time. The relevance of the hydrogen bonding to the mechanism of protonation of metal hydrides is suggested.
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Shubina E. S. et al. Spectroscopic Evidence for Intermolecular M−H···H−OR Hydrogen Bonding: Interaction of WH(CO)2(NO)L2 Hydrides with Acidic Alcohols // Journal of the American Chemical Society. 1996. Vol. 118. No. 5. pp. 1105-1112.
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Shubina E. S., belkova N. V., Krylov A. N., Vorontsov E. V., epstein L. M., Gusev D. G., Niedermann M., Berke H. Spectroscopic Evidence for Intermolecular M−H···H−OR Hydrogen Bonding: Interaction of WH(CO)2(NO)L2 Hydrides with Acidic Alcohols // Journal of the American Chemical Society. 1996. Vol. 118. No. 5. pp. 1105-1112.
Cite this
RIS
Copy
TY - JOUR
DO - 10.1021/ja953094z
UR - https://doi.org/10.1021/ja953094z
TI - Spectroscopic Evidence for Intermolecular M−H···H−OR Hydrogen Bonding: Interaction of WH(CO)2(NO)L2 Hydrides with Acidic Alcohols
T2 - Journal of the American Chemical Society
AU - Shubina, Elena S.
AU - belkova, Natalia V.
AU - Krylov, Aleksandr N
AU - Vorontsov, Evgeni V
AU - epstein, Lina M.
AU - Gusev, Dmitri G
AU - Niedermann, Martina
AU - Berke, Heinz
PY - 1996
DA - 1996/01/01
PB - American Chemical Society (ACS)
SP - 1105-1112
IS - 5
VL - 118
SN - 0002-7863
SN - 1520-5126
ER -
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BibTex (up to 50 authors)
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@article{1996_Shubina,
author = {Elena S. Shubina and Natalia V. belkova and Aleksandr N Krylov and Evgeni V Vorontsov and Lina M. epstein and Dmitri G Gusev and Martina Niedermann and Heinz Berke},
title = {Spectroscopic Evidence for Intermolecular M−H···H−OR Hydrogen Bonding: Interaction of WH(CO)2(NO)L2 Hydrides with Acidic Alcohols},
journal = {Journal of the American Chemical Society},
year = {1996},
volume = {118},
publisher = {American Chemical Society (ACS)},
month = {jan},
url = {https://doi.org/10.1021/ja953094z},
number = {5},
pages = {1105--1112},
doi = {10.1021/ja953094z}
}
Cite this
MLA
Copy
Shubina, Elena S., et al. “Spectroscopic Evidence for Intermolecular M−H···H−OR Hydrogen Bonding: Interaction of WH(CO)2(NO)L2 Hydrides with Acidic Alcohols.” Journal of the American Chemical Society, vol. 118, no. 5, Jan. 1996, pp. 1105-1112. https://doi.org/10.1021/ja953094z.
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