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Title: The Molybdenum(V) and Tungsten(VI) Oxoazides [MoO(N 3 ) 3 ], [MoO(N 3 ) 3 ⋅2 CH 3 CN], [(bipy)MoO(N 3 ) 3 ], [MoO(N 3 ) 5 ] 2− , [WO(N 3 ) 4 ], and [WO(N 3 ) 4 ⋅CH 3 CN]

Journal Article · · Angewandte Chemie (International Edition)

Abstract A series of novel molybdenum(V) and tungsten(VI) oxoazides was prepared starting from [MOF 4 ] (M=Mo, W) and Me 3 SiN 3 . While [WO(N 3 ) 4 ] was formed through fluoride–azide exchange in the reaction of Me 3 SiN 3 with WOF 4 in SO 2 solution, the reaction with MoOF 4 resulted in a reduction of Mo VI to Mo V and formation of [MoO(N 3 ) 3 ]. Carried out in acetonitrile solution, these reactions resulted in the isolation of the corresponding adducts [MoO(N 3 ) 3 ⋅2 CH 3 CN] and [WO(N 3 ) 4 ⋅CH 3 CN]. Subsequent reactions of [MoO(N 3 ) 3 ] with 2,2′‐bipyridine and [PPh 4 ][N 3 ] resulted in the formation and isolation of [(bipy)MoO(N 3 ) 3 ] and [PPh 4 ] 2 [MoO(N 3 ) 5 ], respectively. Most molybdenum(V) and tungsten(VI) oxoazides were fully characterized by their vibrational spectra, impact, friction and thermal sensitivity data and, in the case of [WO(N 3 ) 4 ⋅CH 3 CN], [(bipy)MoO(N 3 ) 3 ], and [PPh 4 ] 2 [MoO(N 3 ) 5 ], by their X‐ray crystal structures.

Sponsoring Organization:
USDOE
OSTI ID:
1813887
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Vol. 54 Journal Issue: 51; ISSN 1433-7851
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (50)

Fluoride crystal structures. Part II. Molybdenum oxide tetrafluoride journal January 1968
First Structural Characterization of Binary AsIII and SbIII Azides journal January 2004
Electron Affinities, Fluoride Affinities, and Heats of Formation of the Second Row Transition Metal Hexafluorides: MF 6 (M = Mo, Tc, Ru, Rh, Pd, Ag) journal June 2010
The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO 2 (N 3 ) 2 , MO 2 (N 3 ) 2 ⋅2 CH 3 CN, (bipy)MO 2 (N 3 ) 2 , and [MO 2 (N 3 ) 4 ] 2− (M=Mo, W) journal July 2015
Why Are [P(C 6 H 5 ) 4 ] + N 3 and [As(C 6 H 5 ) 4 ] + N 3 Ionic Salts and Sb(C 6 H 5 ) 4 N 3 and Bi(C 6 H 5 ) 4 N 3 Covalent Solids? A Theoretical Study Provides an Unexpected Answer journal April 2011
Oxidation, Reduction, and Condensation of Alcohols over (MO 3 ) 3 (M = Mo, W) Nanoclusters journal September 2014
Molpro: a general-purpose quantum chemistry program package: Molpro
  • Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2 https://doi.org/10.1002/wcms.82
journal July 2011
Preparation of the First Manganese(III) and Manganese(IV) Azides journal July 2014
Coordination Adducts of Niobium(V) and Tantalum(V) Azide M(N 3 ) 5 (M=Nb, Ta) with Nitrogen Donor Ligands and their Self-Ionization journal April 2014
Coupled cluster theory for high spin, open shell reference wave functions journal October 1993
A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples journal February 1982
Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis journal August 1980
Energy-consistent relativistic pseudopotentials and correlation consistent basis sets for the 4d elements Y–Pd journal March 2007
Azide Chemistry - An Inorganic Perspective, Part I Metal ­Azides: Overview, General Trends and Recent Developments journal June 2013
COSMO: a new approach to dielectric screening in solvents with explicit expressions for the screening energy and its gradient journal January 1993
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions journal May 1992
Recent Developments in the Chemistry of Covalent Azides journal April 1997
Basis set limit electronic excitation energies, ionization potentials, and electron affinities for the 3d transition metal atoms: Coupled cluster and multireference methods journal August 2006
ShelXle : a Qt graphical user interface for SHELXL journal November 2011
Explosives book July 2007
SHELXT – Integrated space-group and crystal-structure determination journal January 2015
Coupled-cluster theory in quantum chemistry journal February 2007
Quantum Mechanical Continuum Solvation Models journal August 2005
Systematically convergent basis sets for transition metals. I. All-electron correlation consistent basis sets for the 3d elements Sc–Zn journal August 2005
Kovalente anorganische Azide journal March 1995
ORTEP -3 for Windows - a version of ORTEP -III with a Graphical User Interface (GUI) journal October 1997
Optimization of Gaussian-type basis sets for local spin density functional calculations. Part I. Boron through neon, optimization technique and validation journal February 1992
Perturbative corrections to account for triple excitations in closed and open shell coupled cluster theories journal September 1994
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Erratum: “Coupled cluster theory for high spin, open shell reference wave functions” [ J. Chem. Phys. 99 , 5219 (1993)] journal February 2000
Energy-consistent pseudopotentials and correlation consistent basis sets for the 5d elements Hf–Pt journal April 2009
Coordination Adducts of Niobium(V) and Tantalum(V) Azide M(N 3 ) 5 (M=Nb, Ta) with Nitrogen Donor Ligands and their Self-Ionization journal April 2014
A short history of SHELX journal December 2007
Dehydration, dehydrogenation, and condensation of alcohols on supported oxide catalysts based on cyclic (WO 3 ) 3 and (MoO 3 ) 3 clusters journal January 2014
Crystal structure refinement with SHELXL journal January 2015
Polyazide Chemistry: The First Binary Group 6 Azides, Mo(N3)6, W(N3)6, [Mo(N3)7]?, and [W(N3)7]?, and the [NW(N3)4]? and [NMo(N3)4]? Ions journal March 2005
Polyazide Chemistry: Preparation and Characterization of As(N3)5, Sb(N3)5, and [P(C6H5)4][Sb(N3)6] journal December 2004
The Vanadium(V) Oxoazides [VO(N 3 ) 3 ], [(bipy)VO(N 3 ) 3 ], and [VO(N 3 ) 5 ] 2− journal June 2015
The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO 2 (N 3 ) 2 , MO 2 (N 3 ) 2 ⋅2 CH 3 CN, (bipy)MO 2 (N 3 ) 2 , and [MO 2 (N 3 ) 4 ] 2− (M=Mo, W) journal July 2015
Third Row Transition Metal Hexafluorides, Extraordinary Oxidizers, and Lewis Acids: Electron Affinities, Fluoride Affinities, and Heats of Formation of WF 6 , ReF 6 , OsF 6 , IrF 6 , PtF 6 , and AuF 6 journal February 2010
Tetrazido-Nitrido-Molybdat(VI); Darstellung, IR-Spektrum und Kristallstruktur von AsPh4[MoN(N3)4] / Tetrazido-nitrido-molybdate(VI); Preparation, IR Spectrum and Crystal Structure of AsPh4[MoN(N3)4] journal September 1980
Inorganic and Transition Metal Azides journal April 2010
Covalent Inorganic Azides journal March 1995
Preparation of the First Manganese(III) and Manganese(IV) Azides journal July 2014
Coupled‐cluster methods with noniterative triple excitations for restricted open‐shell Hartree–Fock and other general single determinant reference functions. Energies and analytical gradients journal June 1993
Note on an Approximation Treatment for Many-Electron Systems journal October 1934
Fluoride crystal structures. Part I. Tungsten oxide tetrafluoride journal January 1968
Polyazide Chemistry: Preparation and Characterization of As(N3)5, Sb(N3)5, and [P(C6H5)4][Sb(N3)6] journal December 2004
The Vanadium(V) Oxoazides [VO(N 3 ) 3 ], [(bipy)VO(N 3 ) 3 ], and [VO(N 3 ) 5 ] 2− journal June 2015
Polyazide Chemistry: The First Binary Group 6 Azides, Mo(N3)6, W(N3)6, [Mo(N3)7]?, and [W(N3)7]?, and the [NW(N3)4]? and [NMo(N3)4]? Ions journal March 2005