Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 134, Issue 34, Pages 14158-14164Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja305248f
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Funding
- Gordon and Betty Moore Foundation
- NSF Center for Chemical Innovation on Solar Fuels (CCI Solar) [CHE-0802907, CHE-0947829]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0802907] Funding Source: National Science Foundation
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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 CoBr2 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 [SiP3]Co(N-2) (1-N-2) ([SiP3] = 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: Delta H degrees = -12.5(3) kcal mol(-1) and Delta S degrees = -26(3) cal K-1 mol(-1); N-2: Delta H degrees = -13.9(7) kcal mol(-1) and Delta S degrees = -32(5) cal K-1 mol(-1)).
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