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Water Oxidation by the [Co4O4(OAc)4(py)4]+ Cubium is Initiated by OH– Addition

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Text
TitleInfo
Title
Water Oxidation by the [Co4O4(OAc)4(py)4]+ Cubium is Initiated by OH– Addition
Name (type = personal)
NamePart (type = family)
Smith
NamePart (type = given)
Paul F.
Affiliation
Chemistry & Chemical Biology, Rutgers University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Hunt
NamePart (type = given)
Liam
Affiliation
Chemistry & Chemical Biology, Rutgers University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Laursen
NamePart (type = given)
Anders B.
Affiliation
Chemistry & Chemical Biology, Rutgers University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Sagar
NamePart (type = given)
Viral
Affiliation
Chemistry & Chemical Biology, Rutgers University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Kaushik
NamePart (type = given)
Shivam
Affiliation
Chemistry & Chemical Biology, Rutgers University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Calvinho
NamePart (type = given)
Karin U. D.
Affiliation
Chemistry & Chemical Biology, Rutgers University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Marotta
NamePart (type = given)
Gabriele
Affiliation
University of Perugia
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Mosconi
NamePart (type = given)
Edoardo
Affiliation
University of Perugia
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (authority = orcid); (authorityURI = http://id.loc.gov/vocabulary/identifiers/orcid.html); (type = personal); (valueURI = http://orcid.org/0000-0003-3833-1975)
NamePart (type = family)
De Angelis
NamePart (type = given)
Filippo
Affiliation
University of Perugia
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (type = personal)
NamePart (type = family)
Dismukes
NamePart (type = given)
G. Charles
Affiliation
Chemistry & Chemical Biology, Rutgers University
Role
RoleTerm (authority = marcrt); (type = text)
author
Name (authority = RutgersOrg-Department); (type = corporate)
NamePart
Chemistry & Chemical Biology
Name (authority = RutgersOrg-School); (type = corporate)
NamePart
School of Arts and Sciences (SAS) (New Brunswick)
Genre (authority = RULIB-FS)
Article, Refereed
Genre (authority = NISO JAV)
Accepted Manuscript (AM)
OriginInfo
Publisher
ACS Publications
Place
PlaceTerm (type = text)
Washington, D.C.
DateIssued (encoding = w3cdtf); (keyDate = yes); (qualifier = exact)
2015
PhysicalDescription
InternetMediaType
application/pdf
Extent
10 p.
Extension
DescriptiveEvent
Type
Citation
AssociatedObject
Name
Journal of the American Chemical Society
Type
Journal
Relationship
Has part
Reference (type = url)
http://dx.doi.org/10.1021/jacs.5b09152
Identifier (type = volume and issue)
137(49)
Detail
15460-15468
DateTime (encoding = w3cdtf)
2015
Subject (authority = LCSH)
Topic
Oxidation
Subject (authority = local)
Topic
Cobalt cubium
Abstract (type = abstract)
The cobalt cubium Co4O4(OAc)4(py)4(ClO4) (1A+) containing the mixed valence [Co4O4]5+ core is shown by multiple spectroscopic methods to react with hydroxide (OH-) but not with water molecules to produce O2. The yield of reaction products is stoichiometric (>99.5%): 4 1A+ + 4 OH- → O2 + 2 H2O + 4 1A. By contrast, the structurally homologous cubium Co4O4(trans-OAc)2(bpy)4(ClO4)3, 1B(ClO4)3 produces no O2. EPR/NMR spectroscopies show clean conversion to cubane 1A during O2 evolution with no Co2+ or Co3O4 side products. Mass spectrometry of the reaction between isotopically labeled µ-16O(bridging-oxo) 1A+ and 18O-bicarbonate/water shows: 1) no exchange of 18O into the bridging oxos of 1A+, and 2) 36O2 is the major product, thus requiring two OH- in the reactive intermediate. DFT calculations of solvated intermediates suggest that addition of two OH- to 1A+ via OH- insertion into Co-OAc bonds is energetically favored, followed by outer-sphere oxidation to intermediate [1A(OH)2]0. The absence of O2 production by cubium 1B3+ indicates the reactive intermediate derived from 1A+ requires gem-1,1-dihydoxo stereochemistry to perform O-O bond formation. Outer-sphere oxidation of this intermediate by 2 eq. 1A+ accounts for the final stoichiometry. Collectively, these results, and recent literature (Faraday Disc., doi:10.1039/C5FD00076A and J.Am.Chem.Soc 2015, 12865-12872) validate the [Co4O4]4+/5+ cubane core as an intrinsic catalyst for oxidation of hydroxide by an inner-sphere mechanism.
Note (type = version identification)
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://dx.doi.org/10.1021/jacs.5b09152
Note (type = peerReview)
Peer reviewed
RelatedItem (type = host)
TitleInfo
Title
Dismukes, G. Charles
Identifier (type = local)
rucore30183300001
RelatedItem (type = host)
TitleInfo
Title
Laursen, Anders B.
Identifier (type = local)
rucore30183200001
RelatedItem (type = host)
TitleInfo
Title
Smith, Paul F.
Identifier (type = local)
rucore30179200001
Location
PhysicalLocation (authority = marcorg); (displayLabel = Rutgers, The State University of New Jersey)
NjNbRU
Identifier (type = doi)
doi:10.7282/T37P91BG
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Multiple author license v. 1
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RightsEvent
Type
Embargo
DateTime (point = start); (encoding = w3cdtf)
2015-12-02
DateTime (point = end); (encoding = w3cdtf)
2017-01-31
Detail
Access to this PDF has been restricted at the publisher's request.The publisher, ACS Publications, requires a 12 month embargo from the date the article was published. The article in this repository will be publicly available after January 31, 2017.
RightsHolder (type = corporate)
Name
American Chemical Society
Role
Copyright holder
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