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Title: Isolation and X-ray molecular structure of the first oxo- and phosphanido-bridged diniobium(III) complex with a short double Nb = Nb bond. Oxidation of the dichloro(pentamethylcyclopentadienyl)niobium(III) dimer

Abstract

The reaction of [NbCp[sup *]Cl[sub 2]][sub 2], Cp[sup *] = [eta][sup 5]-C[sub 5]Me[sub 5], with 4 equiv of LiP(C[sub 6]H[sub 5])[sub 2] in the presence of water gives [(NbCp[sup *])[sub 2]-([mu]-PPh[sub 2])[sub 2]([mu]-O)] (1). The niobium(III) dimer is transformed in the air and reacts with oxygen to give the already reported oxo complexes [NbCp[sup *]Cl[sub 2](OH)][sub 2]([mu]-O) and (NbCp[sup *])[sub 3]Cl[sub 4]O[sub 4], respectively. An analogous reaction with azobenzene does not allow one to isolate either any hydrazido(2-) or amido derivatives, but in the presence of water the same oxo trimer is formed with elimination of 1,2-diphenylhydrazine. A similar reaction with azobiphenylene give NbCp[sup *]Cl[sub 2](azobiphenylene) (2), which was characterized by mass spectrometry and IR and [sup 1]H and [sup 13]C NMR spectroscopy. The molecular structures of complex 1 was determined by X-ray diffraction methods. Complex 1 crystallizes in the monoclinic space group C2/c, with unit cell dimensions of a = 19.327(8) [angstrom], b = 11.198(2) [angstrom], c = 22.248(9) [angstrom], [beta] = 122.98(2)[degrees], and V = 4039(4) [angstrom][sup 3], with Z = 4 and [rho][sub calcd] = 1.412 g cm[sup [minus]3]. The compound shows a very short double bond Nb=Nb distance of 2.625(5) [angstrom].

Authors:
; ; ;  [1]
  1. (Universidad de Alcala, Alcala de Henares (Spain))
Publication Date:
OSTI Identifier:
6981053
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; (United States); Journal Volume: 32:24
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; NIOBIUM COMPLEXES; MOLECULAR STRUCTURE; OXIDATION; ABSORPTION SPECTROSCOPY; BOND LENGTHS; MASS SPECTROSCOPY; MONOCLINIC LATTICES; NUCLEAR MAGNETIC RESONANCE; ORGANOMETALLIC COMPOUNDS; X-RAY DIFFRACTION; CHEMICAL REACTIONS; COHERENT SCATTERING; COMPLEXES; CRYSTAL LATTICES; CRYSTAL STRUCTURE; DIFFRACTION; DIMENSIONS; LENGTH; MAGNETIC RESONANCE; ORGANIC COMPOUNDS; RESONANCE; SCATTERING; SPECTROSCOPY; TRANSITION ELEMENT COMPLEXES; 400201* - Chemical & Physicochemical Properties

Citation Formats

Mata, J. de la, Gomez, M., Gomez-Sal, P., and Royo, P. Isolation and X-ray molecular structure of the first oxo- and phosphanido-bridged diniobium(III) complex with a short double Nb = Nb bond. Oxidation of the dichloro(pentamethylcyclopentadienyl)niobium(III) dimer. United States: N. p., 1993. Web. doi:10.1021/ic00076a009.
Mata, J. de la, Gomez, M., Gomez-Sal, P., & Royo, P. Isolation and X-ray molecular structure of the first oxo- and phosphanido-bridged diniobium(III) complex with a short double Nb = Nb bond. Oxidation of the dichloro(pentamethylcyclopentadienyl)niobium(III) dimer. United States. doi:10.1021/ic00076a009.
Mata, J. de la, Gomez, M., Gomez-Sal, P., and Royo, P. Wed . "Isolation and X-ray molecular structure of the first oxo- and phosphanido-bridged diniobium(III) complex with a short double Nb = Nb bond. Oxidation of the dichloro(pentamethylcyclopentadienyl)niobium(III) dimer". United States. doi:10.1021/ic00076a009.
@article{osti_6981053,
title = {Isolation and X-ray molecular structure of the first oxo- and phosphanido-bridged diniobium(III) complex with a short double Nb = Nb bond. Oxidation of the dichloro(pentamethylcyclopentadienyl)niobium(III) dimer},
author = {Mata, J. de la and Gomez, M. and Gomez-Sal, P. and Royo, P.},
abstractNote = {The reaction of [NbCp[sup *]Cl[sub 2]][sub 2], Cp[sup *] = [eta][sup 5]-C[sub 5]Me[sub 5], with 4 equiv of LiP(C[sub 6]H[sub 5])[sub 2] in the presence of water gives [(NbCp[sup *])[sub 2]-([mu]-PPh[sub 2])[sub 2]([mu]-O)] (1). The niobium(III) dimer is transformed in the air and reacts with oxygen to give the already reported oxo complexes [NbCp[sup *]Cl[sub 2](OH)][sub 2]([mu]-O) and (NbCp[sup *])[sub 3]Cl[sub 4]O[sub 4], respectively. An analogous reaction with azobenzene does not allow one to isolate either any hydrazido(2-) or amido derivatives, but in the presence of water the same oxo trimer is formed with elimination of 1,2-diphenylhydrazine. A similar reaction with azobiphenylene give NbCp[sup *]Cl[sub 2](azobiphenylene) (2), which was characterized by mass spectrometry and IR and [sup 1]H and [sup 13]C NMR spectroscopy. The molecular structures of complex 1 was determined by X-ray diffraction methods. Complex 1 crystallizes in the monoclinic space group C2/c, with unit cell dimensions of a = 19.327(8) [angstrom], b = 11.198(2) [angstrom], c = 22.248(9) [angstrom], [beta] = 122.98(2)[degrees], and V = 4039(4) [angstrom][sup 3], with Z = 4 and [rho][sub calcd] = 1.412 g cm[sup [minus]3]. The compound shows a very short double bond Nb=Nb distance of 2.625(5) [angstrom].},
doi = {10.1021/ic00076a009},
journal = {Inorganic Chemistry; (United States)},
number = ,
volume = 32:24,
place = {United States},
year = {Wed Nov 24 00:00:00 EST 1993},
month = {Wed Nov 24 00:00:00 EST 1993}
}