Neue Azidokomplexe des Tantals(V). Synthese und Molekülstruktur der Zweikernverbindungen [Cp*TaCl(N3)(μ-N3)]2(μ-O) und [Cp*Ta(N3)3(μ-N3)]2 (Cp* = Pentamethylcyclopentadienyl)

Dedicated to Professor Reint Eujen on the occasion of his 60th birthdayWhereas the existence of numerous binary transition-metalazido complexes has been reported, [1][2][3] no binary Group 5 azides are known. Only a limited number of partially azidosubstituted compounds of vanadium, niobium, and tantalum have previously been reported. [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] Herein, we communicate the synthesis and characterization of [Nb(N 3 When the volatile compounds (SO 2 , (CH 3 ) 3 SiF, and excess (CH 3 ) 3 SiN 3 ) were removed in a vacuum at À20 8C, pure, yellow, solid, room-temperature-stable pentaazido complexes were produced in quantitative yield. As expected for covalently bonded polyazido complexes, [22] 5 ] are shown in the Supporting Information, and the observed frequencies and intensities are listed in the Experimental Section. These data were assigned by comparison with those calculated at the B3LYP [23] and MP2 [24] levels of theory by using SBKJ + (d) basis sets.[25] The agreement between the observed and calculated spectra is satisfactory and supports the existence of trigonal-bipyramidal structures (Table 1)

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Experimental Evidence for Linear Metal–Azido Coordination: The Binary Group 5 Azides [Nb(N₃)₅], [Ta(N₃)₅], [Nb(N₃)₆]⁻, and [Ta(N₃)₆]⁻, and 1:1 Acetonitrile Adducts [Nb(N₃)₅(CH₃CN)] and [Ta(N₃)₅(CH₃CN)]

Haiges

¹

,

Boatz

²

,

Schroer

³

et al. 2006

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Dedicated to Professor Reint Eujen on the occasion of his 60th birthdayWhereas the existence of numerous binary transition-metalazido complexes has been reported, [1][2][3] no binary Group 5 azides are known. Only a limited number of partially azidosubstituted compounds of vanadium, niobium, and tantalum have previously been reported. [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] Herein, we communicate the synthesis and characterization of [Nb(N 3 When the volatile compounds (SO 2 , (CH 3 ) 3 SiF, and excess (CH 3 ) 3 SiN 3 ) were removed in a vacuum at À20 8C, pure, yellow, solid, room-temperature-stable pentaazido complexes were produced in quantitative yield. As expected for covalently bonded polyazido complexes, [22] 5 ] are shown in the Supporting Information, and the observed frequencies and intensities are listed in the Experimental Section. These data were assigned by comparison with those calculated at the B3LYP [23] and MP2 [24] levels of theory by using SBKJ + (d) basis sets.[25] The agreement between the observed and calculated spectra is satisfactory and supports the existence of trigonal-bipyramidal structures (Table 1)

show abstract

Neue Azidokomplexe des Tantals(V). Synthese und Molekülstruktur der Zweikernverbindungen [CpTaCl(N3)(μ-N3)]2(μ-O) und [CpTa(N3)3(μ-N3)]2 (Cp* = Pentamethylcyclopentadienyl)

Cited by 10 publications

References 12 publications

Applications in Coordination Chemistry

Applications in Coordination Chemistry

Experimental Evidence for Linear Metal–Azido Coordination: The Binary Group 5 Azides [Nb(N₃)₅], [Ta(N₃)₅], [Nb(N₃)₆]⁻, and [Ta(N₃)₆]⁻, and 1:1 Acetonitrile Adducts [Nb(N₃)₅(CH₃CN)] and [Ta(N₃)₅(CH₃CN)]

Experimental Evidence for Linear Metal–Azido Coordination: The Binary Group 5 Azides [Nb(N₃)₅], [Ta(N₃)₅], [Nb(N₃)₆]⁻, and [Ta(N₃)₆]⁻, and 1:1 Acetonitrile Adducts [Nb(N₃)₅(CH₃CN)] and [Ta(N₃)₅(CH₃CN)]

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Neue Azidokomplexe des Tantals(V). Synthese und Molekülstruktur der Zweikernverbindungen [Cp*TaCl(N3)(μ-N3)]2(μ-O) und [Cp*Ta(N3)3(μ-N3)]2 (Cp* = Pentamethylcyclopentadienyl)

Cited by 10 publications

References 12 publications

Applications in Coordination Chemistry

Applications in Coordination Chemistry

Experimental Evidence for Linear Metal–Azido Coordination: The Binary Group 5 Azides [Nb(N3)5], [Ta(N3)5], [Nb(N3)6]−, and [Ta(N3)6]−, and 1:1 Acetonitrile Adducts [Nb(N3)5(CH3CN)] and [Ta(N3)5(CH3CN)]

Experimental Evidence for Linear Metal–Azido Coordination: The Binary Group 5 Azides [Nb(N3)5], [Ta(N3)5], [Nb(N3)6]−, and [Ta(N3)6]−, and 1:1 Acetonitrile Adducts [Nb(N3)5(CH3CN)] and [Ta(N3)5(CH3CN)]

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Neue Azidokomplexe des Tantals(V). Synthese und Molekülstruktur der Zweikernverbindungen [CpTaCl(N3)(μ-N3)]2(μ-O) und [CpTa(N3)3(μ-N3)]2 (Cp* = Pentamethylcyclopentadienyl)

Experimental Evidence for Linear Metal–Azido Coordination: The Binary Group 5 Azides [Nb(N₃)₅], [Ta(N₃)₅], [Nb(N₃)₆]⁻, and [Ta(N₃)₆]⁻, and 1:1 Acetonitrile Adducts [Nb(N₃)₅(CH₃CN)] and [Ta(N₃)₅(CH₃CN)]

Experimental Evidence for Linear Metal–Azido Coordination: The Binary Group 5 Azides [Nb(N₃)₅], [Ta(N₃)₅], [Nb(N₃)₆]⁻, and [Ta(N₃)₆]⁻, and 1:1 Acetonitrile Adducts [Nb(N₃)₅(CH₃CN)] and [Ta(N₃)₅(CH₃CN)]