Suess, Daniel L. M. and Tsay, Charlene and Peters, Jonas C. (2012) Dihydrogen Binding to Isostructural S = 1/2 and S = 0 Cobalt Complexes. Journal of the American Chemical Society, 134 (34). pp. 14158-14164. ISSN 0002-7863. doi:10.1021/ja305248f. https://resolver.caltech.edu/CaltechAUTHORS:20120910-104427509
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Abstract
Two isostructural, nonclassical Co(H_2) complexes are prepared from their Co(N_2) precursors using tris(phosphino)silyl and tris(phosphino)borane ancillary ligands. Comproportionation of CoBr_2 and Co metal in the presence of TPB (tris-(o-diisopropylphophinophenyl)borane) gives (TPB)CoBr (4). One-electron reduction of 4 triggers N_2 binding to give (TPB)Co(N_2) (2-N_2) which is isostructural to previously reported [SiP_3]Co(N_2) (1-N_2) ([SiP_3] = tris-(o-diisopropylphosphinophenyl)silyl). Both 1-N_2 and 2-N_2 react with 1 atm H_2 to generate thermally stable H_2 complexes 1-H_2 and 2-H_2, respectively. Both complexes are characterized by a suite of spectroscopic techniques in solution and by X-ray crystallography. The H_2 and N_2 ligands in 2-H_2 and 2-N_2 are labile under ambient conditions and the binding equilibria are observable by temperature-dependent UV/vis. A van’t Hoff analysis allows for the ligand binding energetics to be determined (H_2: ΔHº = −12.5(3) kcal mol^(–1) and ΔSº = −26(3) cal K^(–1) mol^(–1); N_2: ΔHº = −13.9(7) kcal mol^(–1) and ΔSº = −32(5) cal K^(–1) mol^(–1)).
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Additional Information: | © 2012 American Chemical Society. Received: May 30, 2012. Publication Date (Web): August 14, 2012. We thank the Gordon and Betty Moore Foundation and the NSF Center for Chemical Innovation on Solar Fuels (CCI Solar, CHE-0802907 and CHE-0947829) for funding. We thank Prof. George Rossman (solid-state Raman studies), Maraia Ener (solution-state Raman studies), and Lawrence Henling (X-ray crystallography) for experimental assistance. | ||||||||
Group: | CCI Solar Fuels | ||||||||
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Issue or Number: | 34 | ||||||||
DOI: | 10.1021/ja305248f | ||||||||
Record Number: | CaltechAUTHORS:20120910-104427509 | ||||||||
Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20120910-104427509 | ||||||||
Official Citation: | Dihydrogen Binding to Isostructural S = 1/2 and S = 0 Cobalt Complexes Daniel L. M. Suess, Charlene Tsay, and Jonas C. Peters Journal of the American Chemical Society 2012 134 (34), 14158-14164 | ||||||||
Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||||
ID Code: | 33959 | ||||||||
Collection: | CaltechAUTHORS | ||||||||
Deposited By: | Ruth Sustaita | ||||||||
Deposited On: | 10 Sep 2012 18:08 | ||||||||
Last Modified: | 09 Nov 2021 23:05 |
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