Oxygen reduction to water mediated by a dirhodium hydrido-chloride complex

Thomas S. Teets; Timothy R. Cook; Brian D. McCarthy; Daniel G. Nocera

doi:10.1021/ja201972v

Oxygen reduction to water mediated by a dirhodium hydrido-chloride complex

Thomas S. Teets
, Timothy R. Cook
, Brian D. McCarthy
, Daniel G. Nocera

Chemistry

Massachusetts Institute of Technology

Research output: Contribution to journal › Article › peer-review

42 Scopus citations

Abstract

The two-electron mixed-valence dirhodium complex Rh₂ ^0,II(tfepma)₂(CN^tBu)₂Cl₂ (tfepma = CH₃N[P(OCH₂CF₃)₂] ₂) reacts with HCl to furnish two isomeric dirhodium hydrido-chloride complexes, Rh₂^II,II(tfepma)₂(CN ^tBu)₂Cl₃H. In the presence of HCl, the hydride complex effects the reduction of 0.5 equiv of O₂ to 1 equiv of H ₂O, generating Rh₂^II,II(tfepma) ₂(CN^tBu)₂Cl₄, which can be prepared independently by chlorine oxidation of the Rh₂^0,II precursor. The starting Rh₂^0,II complex is regenerated photochemically to close an oxygen-to-water reduction photocycle.

Original language	English
Pages (from-to)	8114-8117
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	133
Issue number	21
DOIs	https://doi.org/10.1021/ja201972v
State	Published - Jun 1 2011

Access to Document

10.1021/ja201972v

Cite this

@article{459b0e38f1b34e41b7f896131bc40c4d,

title = "Oxygen reduction to water mediated by a dirhodium hydrido-chloride complex",

abstract = "The two-electron mixed-valence dirhodium complex Rh2 0,II(tfepma)2(CNtBu)2Cl2 (tfepma = CH3N[P(OCH2CF3)2] 2) reacts with HCl to furnish two isomeric dirhodium hydrido-chloride complexes, Rh2II,II(tfepma)2(CN tBu)2Cl3H. In the presence of HCl, the hydride complex effects the reduction of 0.5 equiv of O2 to 1 equiv of H 2O, generating Rh2II,II(tfepma) 2(CNtBu)2Cl4, which can be prepared independently by chlorine oxidation of the Rh20,II precursor. The starting Rh20,II complex is regenerated photochemically to close an oxygen-to-water reduction photocycle.",

author = "Teets, \{Thomas S.\} and Cook, \{Timothy R.\} and McCarthy, \{Brian D.\} and Nocera, \{Daniel G.\}",

year = "2011",

month = jun,

day = "1",

doi = "10.1021/ja201972v",

language = "English",

volume = "133",

pages = "8114--8117",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "21",

}

TY - JOUR

T1 - Oxygen reduction to water mediated by a dirhodium hydrido-chloride complex

AU - Teets, Thomas S.

AU - Cook, Timothy R.

AU - McCarthy, Brian D.

AU - Nocera, Daniel G.

PY - 2011/6/1

Y1 - 2011/6/1

N2 - The two-electron mixed-valence dirhodium complex Rh2 0,II(tfepma)2(CNtBu)2Cl2 (tfepma = CH3N[P(OCH2CF3)2] 2) reacts with HCl to furnish two isomeric dirhodium hydrido-chloride complexes, Rh2II,II(tfepma)2(CN tBu)2Cl3H. In the presence of HCl, the hydride complex effects the reduction of 0.5 equiv of O2 to 1 equiv of H 2O, generating Rh2II,II(tfepma) 2(CNtBu)2Cl4, which can be prepared independently by chlorine oxidation of the Rh20,II precursor. The starting Rh20,II complex is regenerated photochemically to close an oxygen-to-water reduction photocycle.

AB - The two-electron mixed-valence dirhodium complex Rh2 0,II(tfepma)2(CNtBu)2Cl2 (tfepma = CH3N[P(OCH2CF3)2] 2) reacts with HCl to furnish two isomeric dirhodium hydrido-chloride complexes, Rh2II,II(tfepma)2(CN tBu)2Cl3H. In the presence of HCl, the hydride complex effects the reduction of 0.5 equiv of O2 to 1 equiv of H 2O, generating Rh2II,II(tfepma) 2(CNtBu)2Cl4, which can be prepared independently by chlorine oxidation of the Rh20,II precursor. The starting Rh20,II complex is regenerated photochemically to close an oxygen-to-water reduction photocycle.

UR - https://www.scopus.com/pages/publications/79957775907

U2 - 10.1021/ja201972v

DO - 10.1021/ja201972v

M3 - Article

AN - SCOPUS:79957775907

SN - 0002-7863

VL - 133

SP - 8114

EP - 8117

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 21

ER -

Oxygen reduction to water mediated by a dirhodium hydrido-chloride complex

Abstract

Access to Document

Other files and links

Fingerprint

Cite this