The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO2(N3)2, MO2(N3)2•2CH3CN, (bipy)MO2(N3)2, and [MO2(N3)4]2- (M=Mo, W)

Ralf Haiges; Juri Skotnitzki; Zongtang Fang; David A. Dixon; Karl O. Christe

doi:10.1002/anie.201504629

The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO₂(N₃)₂, MO₂(N₃)₂•2CH₃CN, (bipy)MO₂(N₃)₂, and [MO₂(N₃)₄]^2- (M=Mo, W)

Ralf Haiges
, Juri Skotnitzki
, Zongtang Fang
, David A. Dixon
, Karl O. Christe

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

9 Scopus citations

Abstract

Molybdenum(VI) and tungsten(VI) dioxodiazide, MO₂(N₃)₂ (M=Mo, W), were prepared through fluoride-azide exchange reactions between MO₂F₂ and Me₃SiN₃ in SO₂ solution. In acetonitrile solution, the fluoride-azide exchange resulted in the isolation of the adducts MO₂(N₃)₂•2 CH₃CN. The subsequent reaction of MO₂(N₃)₂ with 2,2′-bipyridine (bipy) gave the bipyridine adducts (bipy)MO₂(N₃)₂. The hydrolysis of (bipy)MoO₂(N₃)₂ resulted in the formation and isolation of [(bipy)MoO₂N₃]₂O. The tetraazido anions [MO₂(N₃)₄]^2- were obtained by the reaction of MO₂(N₃)₂ with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO₂(N₃)₂, (bipy)WO₂(N₃)₂, [PPh₄]₂[MoO₂(N₃)₄], [PPh₄]₂[WO₂(N₃)₄], and [(bipy)MoO₂N₃]₂O by their X-ray crystal structures. A fluoride-azide exchange enables the preparation of the first molybdenum(VI) and tungsten(VI) oxoazides MO₂(N₃)₂ (M=Mo, W) from MO₂F₂ and Me₃SiN₃ as very friction- and impact-sensitive solids. The reactions of MO₂(N₃)₂ with 2,2′-bipyridine (bipy) and PPh₄N₃ afforded (bipy)MO₂(N₃)₂ and [PPh₄]₂[MO₂(N₃)₄], which were characterized by their X-ray crystal structures.

Original language	English
Pages (from-to)	9581-9585
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	54
Issue number	33
DOIs	https://doi.org/10.1002/anie.201504629
State	Published - Aug 1 2015
Externally published	Yes

Keywords

crystal structures
molybdenum
oxoazides
polyazides
tungsten

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10.1002/anie.201504629

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@article{d5adde34173f4bc7a8a824a32dbf7050,

title = "The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO2(N3)2, MO2(N3)2•2CH3CN, (bipy)MO2(N3)2, and [MO2(N3)4]2- (M=Mo, W)",

abstract = "Molybdenum(VI) and tungsten(VI) dioxodiazide, MO2(N3)2 (M=Mo, W), were prepared through fluoride-azide exchange reactions between MO2F2 and Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride-azide exchange resulted in the isolation of the adducts MO2(N3)2•2 CH3CN. The subsequent reaction of MO2(N3)2 with 2,2′-bipyridine (bipy) gave the bipyridine adducts (bipy)MO2(N3)2. The hydrolysis of (bipy)MoO2(N3)2 resulted in the formation and isolation of [(bipy)MoO2N3]2O. The tetraazido anions [MO2(N3)4]2- were obtained by the reaction of MO2(N3)2 with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO2(N3)2, (bipy)WO2(N3)2, [PPh4]2[MoO2(N3)4], [PPh4]2[WO2(N3)4], and [(bipy)MoO2N3]2O by their X-ray crystal structures. A fluoride-azide exchange enables the preparation of the first molybdenum(VI) and tungsten(VI) oxoazides MO2(N3)2 (M=Mo, W) from MO2F2 and Me3SiN3 as very friction- and impact-sensitive solids. The reactions of MO2(N3)2 with 2,2′-bipyridine (bipy) and PPh4N3 afforded (bipy)MO2(N3)2 and [PPh4]2[MO2(N3)4], which were characterized by their X-ray crystal structures.",

keywords = "crystal structures, molybdenum, oxoazides, polyazides, tungsten",

author = "Ralf Haiges and Juri Skotnitzki and Zongtang Fang and Dixon, \{David A.\} and Christe, \{Karl O.\}",

note = "Publisher Copyright: {\textcopyright} 2015 WILEY-VCH Verlag GmbH \& Co. KGaA, Weinheim.",

year = "2015",

month = aug,

day = "1",

doi = "10.1002/anie.201504629",

language = "English",

volume = "54",

pages = "9581--9585",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "33",

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TY - JOUR

T1 - The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO2(N3)2, MO2(N3)2•2CH3CN, (bipy)MO2(N3)2, and [MO2(N3)4]2- (M=Mo, W)

AU - Haiges, Ralf

AU - Skotnitzki, Juri

AU - Fang, Zongtang

AU - Dixon, David A.

AU - Christe, Karl O.

PY - 2015/8/1

Y1 - 2015/8/1

N2 - Molybdenum(VI) and tungsten(VI) dioxodiazide, MO2(N3)2 (M=Mo, W), were prepared through fluoride-azide exchange reactions between MO2F2 and Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride-azide exchange resulted in the isolation of the adducts MO2(N3)2•2 CH3CN. The subsequent reaction of MO2(N3)2 with 2,2′-bipyridine (bipy) gave the bipyridine adducts (bipy)MO2(N3)2. The hydrolysis of (bipy)MoO2(N3)2 resulted in the formation and isolation of [(bipy)MoO2N3]2O. The tetraazido anions [MO2(N3)4]2- were obtained by the reaction of MO2(N3)2 with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO2(N3)2, (bipy)WO2(N3)2, [PPh4]2[MoO2(N3)4], [PPh4]2[WO2(N3)4], and [(bipy)MoO2N3]2O by their X-ray crystal structures. A fluoride-azide exchange enables the preparation of the first molybdenum(VI) and tungsten(VI) oxoazides MO2(N3)2 (M=Mo, W) from MO2F2 and Me3SiN3 as very friction- and impact-sensitive solids. The reactions of MO2(N3)2 with 2,2′-bipyridine (bipy) and PPh4N3 afforded (bipy)MO2(N3)2 and [PPh4]2[MO2(N3)4], which were characterized by their X-ray crystal structures.

AB - Molybdenum(VI) and tungsten(VI) dioxodiazide, MO2(N3)2 (M=Mo, W), were prepared through fluoride-azide exchange reactions between MO2F2 and Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride-azide exchange resulted in the isolation of the adducts MO2(N3)2•2 CH3CN. The subsequent reaction of MO2(N3)2 with 2,2′-bipyridine (bipy) gave the bipyridine adducts (bipy)MO2(N3)2. The hydrolysis of (bipy)MoO2(N3)2 resulted in the formation and isolation of [(bipy)MoO2N3]2O. The tetraazido anions [MO2(N3)4]2- were obtained by the reaction of MO2(N3)2 with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO2(N3)2, (bipy)WO2(N3)2, [PPh4]2[MoO2(N3)4], [PPh4]2[WO2(N3)4], and [(bipy)MoO2N3]2O by their X-ray crystal structures. A fluoride-azide exchange enables the preparation of the first molybdenum(VI) and tungsten(VI) oxoazides MO2(N3)2 (M=Mo, W) from MO2F2 and Me3SiN3 as very friction- and impact-sensitive solids. The reactions of MO2(N3)2 with 2,2′-bipyridine (bipy) and PPh4N3 afforded (bipy)MO2(N3)2 and [PPh4]2[MO2(N3)4], which were characterized by their X-ray crystal structures.

KW - crystal structures

KW - molybdenum

KW - oxoazides

KW - polyazides

KW - tungsten

UR - https://www.scopus.com/pages/publications/84938319544

U2 - 10.1002/anie.201504629

DO - 10.1002/anie.201504629

M3 - Article

AN - SCOPUS:84938319544

SN - 1433-7851

VL - 54

SP - 9581

EP - 9585

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 33

ER -

The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO₂(N₃)₂, MO₂(N₃)₂•2CH₃CN, (bipy)MO₂(N₃)₂, and [MO₂(N₃)₄]^2- (M=Mo, W)

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