Homoleptic Azidometalates

Kornath, Andreas

doi:10.1002/1521-3773(20010903)40:17<3135::aid-anie3135>3.0.co;2-b

Cited by 43 publications

(4 citation statements)

References 37 publications

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“…It is obvious that the same stoichiometry leads to a tetra-azide structure, M(N 3 ) 4 , still binding 12 nitrogen atoms to a single metal atom. Although azides are known for most groups of the periodic table, − the group 4 ones seem to be unknown so far. Therefore, their heats of formation and properties would be potentially interesting.…”

Section: Introductionmentioning

confidence: 99%

Predicted Group 4 Tetra-azides M(N₃)₄(M = Ti−Hf, Th): The First Examples of Linear M−NNN Coordination

Gagliardi

Pyykkö

2003

Inorg. Chem.

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Quantum chemical calculations suggest that group 4 tetra-azides M(N 3 ) 4 , where M ) Ti, Zr, Hf, and Th, are stable species. They present a unique structural feature; namely, the M−N−N−N fragments are linear. These species are energetically more stable than the corresponding isomers with general formula η 5 -N 5 −M−η 7 -N 7 , and the Th species, Th(N 3 ) 4 , is the most stable of all. Possible mixed nitride azides NMN 3 were also investigated.

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Section: Introductionmentioning

confidence: 99%

Predicted Group 4 Tetra-azides M(N₃)₄(M = Ti−Hf, Th): The First Examples of Linear M−NNN Coordination

Gagliardi

Pyykkö

2003

Inorg. Chem.

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“…The anion [Si(N 3 ) 6 ] 2- belongs to a class of very rare hypercoordinate silicon complexes with a SiN 6 coordination polyhedron, , and has the highest nitrogen content (89.98%) among the homoleptic hexaazidometalates reported thus far . Further studies in this direction show that stable neutral Lewis-base adducts of Si(N 3 ) 4 are also accessible following a similar approach.…”

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confidence: 99%

The Hexaazidosilicate(IV) Ion: Synthesis, Properties, and Molecular Structure

2002

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The reaction of SiCl4 with an excess of (PPN)N3 (PPN+ = [(Ph3P)2N]+) affords selectively (PPN)2[Si(N3)6] (1). Simultaneous thermal analysis (TG-DTA) shows that the hexaazidosilicate salt is remarkably stable, melting at Tonex = 214 degrees C. Melting of 1 is followed by two distinct exothermic decomposition processes at Ton = 256 and 321 degrees C, the first one involving elimination of N2 and the second one degradation of the PPN cations and evolution of Si(N3)4, N2, and some HN3. The crystal structure of 1 consists of discrete PPN+ cations and S2 symmetric [Si(N3)6]2- anions, which have a very rare, octahedral SiN6 framework and the highest nitrogen content (90%) among the hexaazidometallates reported so far. The IR, Raman, 29Si, and 14N NMR spectra of 1 in CH3CN suggest in combination with the calculated spectra the presence of intact [Si(N3)6]2--anions of S6 symmetry in solution. Geometry optimizations with various methods and basis sets show an S6 symmetric structure to be the most stable [Si(N3)6]2- isomer, the calculated bonding parameters comparing well with the experimental values.

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“…A less dangerous possibility to synthesize the azido complexes is the reaction with Me 3 SiN 3 . For example the reaction of WCl 6 with Me 3 SiN 3 yields WCl 5 N 3 [4], and the hexafluorides of molybdenum and tungsten react with Me 3 SiN 3 to afford the azides M(N 3 ) 6 [5]. [8].…”

Section: Nitrido Complexes and Nitridesmentioning

confidence: 99%

Reactions of Transition Metal Azido Complexes and their Reaction Products

Strähle

2007

Zeitschrift anorg allge chemie

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Transition metal azido complexes can undergo various reactions of their azido group to yield interesting products. The cleavage of the Naα‐Nβ bond and elimination of molecular nitrogen can generate nitrido complexes like MoNCl3 or WNCl3, chloroiminato complexes like Cl3VNCl, or phosphoraneiminato complexes like [Cl4NbNPPh3]2 with metal nitrogen multiple bonds. The reductive elimination of the complete azido group on the other hand may produce metal(0) fragments which in case of gold(I) azido complexes can combine to form clusters.

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Homoleptic Azidometalates

Abstract: Azidometalates are not explosive if the solid salts contain sufficiently large cations. Structure determinations on single crystals of such compounds elucidate how the azide ions (see picture) act as covalently bound ligands and have several different bridging modes.

Cited by 43 publications

References 37 publications

Predicted Group 4 Tetra-azides M(N₃)₄(M = Ti−Hf, Th): The First Examples of Linear M−NNN Coordination

Predicted Group 4 Tetra-azides M(N₃)₄(M = Ti−Hf, Th): The First Examples of Linear M−NNN Coordination

The Hexaazidosilicate(IV) Ion: Synthesis, Properties, and Molecular Structure

Reactions of Transition Metal Azido Complexes and their Reaction Products

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Homoleptic Azidometalates

Abstract: Azidometalates are not explosive if the solid salts contain sufficiently large cations. Structure determinations on single crystals of such compounds elucidate how the azide ions (see picture) act as covalently bound ligands and have several different bridging modes.

Cited by 43 publications

References 37 publications

Predicted Group 4 Tetra-azides M(N3)4(M = Ti−Hf, Th): The First Examples of Linear M−NNN Coordination

Predicted Group 4 Tetra-azides M(N3)4(M = Ti−Hf, Th): The First Examples of Linear M−NNN Coordination

The Hexaazidosilicate(IV) Ion: Synthesis, Properties, and Molecular Structure

Reactions of Transition Metal Azido Complexes and their Reaction Products

Contact Info

Product

Resources

About

Predicted Group 4 Tetra-azides M(N₃)₄(M = Ti−Hf, Th): The First Examples of Linear M−NNN Coordination

Predicted Group 4 Tetra-azides M(N₃)₄(M = Ti−Hf, Th): The First Examples of Linear M−NNN Coordination