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Title: Selective deoxygenation of nitrate to nitrosyl using trivalent chromium and the Mashima reagent: reductive silylation

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/C8SC02979B· OSTI ID:1478435
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Indiana University, Department of Chemistry, Bloomington, USA
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1,4-Bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadiene is an effective silyl transfer reagent towards the oxygen of nitrate coordinated to Cr(III) in a pincer complex. Two nitrate oxygens are removed to give the 17 valence electron octahedral complex (H2L)Cr(NO3)2(NO). This is shown by a variety of spectroscopic methods, together with DFT, to be a Cr(I) complex with a linear CrNO unit. This work also identifies future applications of this reductive silylation process.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Organization:
USDOE Office of Science (SC); Indiana University; National Science Foundation (NSF)
Grant/Contract Number:
AC02-06CH11357; CHE-1362127; CHE-1346572
OSTI ID:
1478435
Alternate ID(s):
OSTI ID: 1491899
Journal Information:
Chemical Science, Journal Name: Chemical Science Vol. 10 Journal Issue: 2; ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)Copyright Statement
Country of Publication:
United Kingdom
Language:
English
Citation Metrics:
Cited by: 20 works
Citation information provided by
Web of Science

References (43)

Molecular and electronic structure of electron-transfer active main-group organometallics journal March 1989
Zur strukturellen flexibilität der “antiaromatischen” 1,4- dihydropyrazine. Kristall- und molekülstrukturen metallorganischer derivate journal December 1985
A 17 electron chromium complex having both nitrosyl and unidentate nitrito ligands. The crystal and molecular structure of dinitritonitrosyltripyridinechromium monopyridine solvate, (ONO)2(NO)(C5H5N)3Cr·C5H5N [1] journal January 1977
Isomerism in nitrosyl-isocyanide complexes of chromium of the types [Cr(NO)(CNR)3(L-L)]n+ and [Cr(NO)(CNR)4(L)]n+ journal March 1985
Novel mixed-ligand cyanonitrosyl [CrNO]5 chelates of chromium(I) with some biologically important 5-chloro-7-iodo-8-hydroxyquinoline sulphonamides journal December 1992
1,4-Bis(trimethylsilyl)-1,4-diaza-2,5-cyclohexadienes as Strong Salt-Free Reductants for Generating Low-Valent Early Transition Metals with Electron-Donating Ligands journal March 2014
Reductive nitrosylation of tetraoxometallates. Part VIII1. A virtually single step synthesis of azido-nitrosyl derivatives of chromium(I) directly from chromate in aqueous-aerobic media. journal January 1983
CO Oxidation and NO Reduction on Metal Surfaces: Density Functional Theory Investigations journal April 2004
Selective Nitrite Reduction at Heterobimetallic CoMg Complexes journal July 2013
Synthesis and structural characterization of an air-stable 17-electron complex containing the {Cr(NO)}2+ core journal January 1990
Hydroxylamine complexes of chromium. The crystal structure of diaquanitrosyl(pyridine-2,6-dicarboxylato)chromium journal November 1984
Mixed nitrosyl-isocyanide-phosphine complexes of chromium(I) and chromium(0): synthesis, characterization, and redox chemistry journal October 1983
Chemical bonding and electronic structure in the ionic species CrNO2 and [Cr(H2O)5NO]2+ by all electron ab initio multi configurations self consistent field calculations journal February 1995
Crystal and molecular structure of tris(ethylenediamine)cobalt pentacyanonitrosylchromate dihydrate, [Co(C2H8N2)3][Cr(CN)5(NO)].2H2O journal November 1970
Boron-mediated activation of carbon dioxide journal February 2016
Inorganic-Salt-Free Reduction in Main-Group Chemistry: Synthesis of a Dibismuthene and a Distibene journal March 2017
Electron Paramagnetic Resonance Studies of Nitrosyl and Thionitrosyl and Density Functional Theory Studies of Nitrido, Nitrosyl, Thionitrosyl, and Selenonitrosyl Complexes of Chromium journal October 2010
Crystal structure, optical, magnetic, and photochemical properties of the complex pentakis(dimethyl sulfoxide)nitrosylchromium(2+) hexafluorophosphate journal April 2009
Definition of corresponding orbitals and the diradical character in broken symmetry DFT calculations on spin coupled systems journal April 2004
Low Temperature Activation of Supported Metathesis Catalysts by Organosilicon Reducing Agents journal August 2016
Dehalogenation of vicinal dihalo compounds by 1,1′-bis(trimethylsilyl)-1 H ,1′ H -4,4′-bipyridinylidene for giving alkenes and alkynes in a salt-free manner journal January 2017
Nitrite reduction by a pyridinediimine complex with a proton-responsive secondary coordination sphere journal January 2016
Reduction of ( t BuN═)NbCl 3 (py) 2 in a Salt-Free Manner for Generating Nb(IV) Dinuclear Complexes and Their Reactivity toward Benzo[ c ]cinnoline journal May 2015
Electron Spin Relaxation in Chromium−Nitrosyl Complexes journal June 1999
Photoinduced Oxygen Transfer and Double-Linkage Isomerism in acis-(NO)(NO2) Transition-Metal Complex by Photocrystallography, FT-IR Spectroscopy and DFT Calculations journal December 2005
Metal-centered oxygen atom transfer reactions journal December 1987
Uncoupled Redox-Inactive Lewis Acids in the Secondary Coordination Sphere Entice Ligand-Based Nitrite Reduction journal April 2018
A bioinspired iron catalyst for nitrate and perchlorate reduction journal November 2016
X-ray Absorption Spectroscopic Studies of Chromium Nitroso Complexes. Crystal and Molecular Structure of (Ph 4 P) 3 [Cr(NO)(NCS) 5 ]·2.4(CH 3 ) 2 CO journal August 2003
Determination of chromium valence over the range Cr(0)–Cr(VI) by electron energy loss spectroscopy journal May 2006
Electronic structure of 1,4-dihydro-1,2,4,5-tetrazines and of related 1,4-dihydroaromatic compounds journal January 1985
Oxygen and chlorine atom transfer between tungsten, molybdenum, and rhenium complexes. Competition between one- and two-electron pathways journal October 1992
A flexible, redox-active macrocycle enables the electrocatalytic reduction of nitrate to ammonia by a cobalt complex journal January 2018
Synthesis of a terminal Ce( iv ) oxo complex by photolysis of a Ce( iii ) nitrate complex journal January 2017
Synthetic Analogues and Reaction Systems Relevant to the Molybdenum and Tungsten Oxotransferases journal February 2004
Powering denitrification: the perspectives of electrocatalytic nitrate reduction journal January 2012
Organometallic nitrosyl chemistry. 49. An unusual 17-electron organometallic radical, CpCr(NO)(PPh3)(CH2SiMe3) journal August 1991
Korrelation zwischen struktur und elektronentransferverhalten metallorganischer modellverbindungen für flavine mit “butterfly”-konformation journal September 1993
Organometall-stabilisierte 1,4-Dihydropyrazine: Extrem elektronenreiche Heterocyclen journal July 1981
Silica-supported isolated molybdenum di-oxo species: formation and activation with organosilicon agent for olefin metathesis journal January 2018
An Earth-system perspective of the global nitrogen cycle journal January 2008
Salt-Free Reduction of Nonprecious Transition-Metal Compounds: Generation of Amorphous Ni Nanoparticles for Catalytic C-C Bond Formation journal September 2015
Stereochemical control of valence. 5. Comparison of the molecular and electronic structures of five- and six-coordinate o-phenylenebis(dimethylarsine) complexes of the {FeNO}7 group journal March 1977

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