Conformational Flexibility of Dibenzobarrelene-Based PC(sp3)P Pincer Iridium Hydride Complexes: The Role of Hemilabile Functional Groups and External Coordinating Solvents
Тип публикации: Journal Article
Дата публикации: 2014-10-15
scimago Q2
wos Q1
БС1
SJR: 0.676
CiteScore: 5.1
Impact factor: 2.9
ISSN: 02767333, 15206041
Organic Chemistry
Inorganic Chemistry
Physical and Theoretical Chemistry
Краткое описание
Bifunctional dibenzobarrelene-based PC(sp3)P pincer iridium complex 1 is known as an efficient catalyst in acceptorless dehydrogenation of alcohols and hydrogenation/hydroformylation of alkenes. In order to shed light on the mechanism of the hydrogen formation/activation, we performed variable-temperature IR and NMR (1H, 31P) analysis of intra- and intermolecular interactions involving a hydride ligand and hydroxymethyl cooperating group in 1 and its analogues. The results of the spectroscopic measurements in different media (dichloromethane, toluene, DMSO, and mixed solvents) were compared with the quantum chemical (DFT/M06 and B3PW91) calculations. The obtained data imply flexibility of the dibenzobarrelene-based scaffold, unprecedented for conventional pincer ligands. Both the CH2OH-substituted complex 1 and its COOEt analogue 3 prefer facial configuration of the PCP ligand with a P–Ir–P angle of ca. 100°. Such geometries are stabilized by Ir···O interaction with the dangling functional group and diffe...
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Silantyev G. A. et al. Conformational Flexibility of Dibenzobarrelene-Based PC(sp3)P Pincer Iridium Hydride Complexes: The Role of Hemilabile Functional Groups and External Coordinating Solvents // Organometallics. 2014. Vol. 33. No. 21. pp. 5964-5973.
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Silantyev G. A., Filippov O. A., Musa S., Gelman D., belkova N. V., Weisz K., epstein L. M., Shubina E. S. Conformational Flexibility of Dibenzobarrelene-Based PC(sp3)P Pincer Iridium Hydride Complexes: The Role of Hemilabile Functional Groups and External Coordinating Solvents // Organometallics. 2014. Vol. 33. No. 21. pp. 5964-5973.
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TY - JOUR
DO - 10.1021/om500308g
UR - https://doi.org/10.1021/om500308g
TI - Conformational Flexibility of Dibenzobarrelene-Based PC(sp3)P Pincer Iridium Hydride Complexes: The Role of Hemilabile Functional Groups and External Coordinating Solvents
T2 - Organometallics
AU - Silantyev, Gleb A
AU - Filippov, Oleg A.
AU - Musa, Sanaa
AU - Gelman, Dmitri
AU - belkova, Natalia V.
AU - Weisz, Klaus
AU - epstein, Lina M.
AU - Shubina, Elena S.
PY - 2014
DA - 2014/10/15
PB - American Chemical Society (ACS)
SP - 5964-5973
IS - 21
VL - 33
SN - 0276-7333
SN - 1520-6041
ER -
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@article{2014_Silantyev,
author = {Gleb A Silantyev and Oleg A. Filippov and Sanaa Musa and Dmitri Gelman and Natalia V. belkova and Klaus Weisz and Lina M. epstein and Elena S. Shubina},
title = {Conformational Flexibility of Dibenzobarrelene-Based PC(sp3)P Pincer Iridium Hydride Complexes: The Role of Hemilabile Functional Groups and External Coordinating Solvents},
journal = {Organometallics},
year = {2014},
volume = {33},
publisher = {American Chemical Society (ACS)},
month = {oct},
url = {https://doi.org/10.1021/om500308g},
number = {21},
pages = {5964--5973},
doi = {10.1021/om500308g}
}
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MLA
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Silantyev, Gleb A., et al. “Conformational Flexibility of Dibenzobarrelene-Based PC(sp3)P Pincer Iridium Hydride Complexes: The Role of Hemilabile Functional Groups and External Coordinating Solvents.” Organometallics, vol. 33, no. 21, Oct. 2014, pp. 5964-5973. https://doi.org/10.1021/om500308g.
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