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Title: Trialkoxynitridomolybdenum compounds: (RO)/sub 3/Mo identical with N. Preparation, structures (R = t-Bu and i-Pr), and comparisons with a tungsten analogue (R = t-Bu)

Abstract

The compound (t-BuO)/sub 3/Mo identical with N is formed in the reaction between Cl/sub 3/Mo identical with N and LiO-t-Bu (3 equiv) in THF and is obtained as a white crystalline compound by either sublimation (85/sup 0/C, 5 x 10/sup -3/ torr) or recrystallization from toluene. In the solid state the compound forms a linear polymer ((t-BuO)/sub 3/Mo identical with N) involving alternating short, 1.66 (1) A, and long, 2.86 (2) A, Mo-N bonds, corresponding formally to triple and weak dative bonds, respectively. In benzene solution, a cryoscopic molecular weight determination indicates the monomeric species is present. The solubilities of the compounds ((t-BuO)/sub 3/M identical with N) where M = Mo and W differ quite markedly, with the molybdenum compound being appreciably more soluble in aromatic solvents. It is suggested that this results from different M identical with N - M bonding along the infinite chain with the tungsten compound having a more basic or nucleophilic nitrogen atom. This suggestion finds support from MO calculations employing the Fenske-Hall method. The W identical with N distance is significantly longer (1.740 (15) A) and the W-N distance shorter (2.661 (15) A). Furthermore, the molybdenum and tungsten compounds differ in their reactivity towardmore » alcohols, yielding, respectively, (RO)/sub 3/Mo identical with N and W(OR)/sub 6/ (R = i-Pr, neo-Pe, Et) and ammonia. These results are compared with other nitrido compounds of molybdenum and tungsten. Crystal data for (t-BuO)/sub 3/Mo identical with N is presented. 19 references, 3 figures, 4 tables.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
E.I. du Pont de Nemours and Co., Inc., Wilmington, DE
OSTI Identifier:
6970928
Resource Type:
Journal Article
Journal Name:
Inorg. Chem.; (United States)
Additional Journal Information:
Journal Volume: 25:23
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALKOXY RADICALS; CHEMICAL PREPARATION; CRYSTAL STRUCTURE; MOLECULAR STRUCTURE; MOLYBDENUM COMPOUNDS; NITRIDES; ORGANOMETALLIC COMPOUNDS; EXPERIMENTAL DATA; TUNGSTEN COMPOUNDS; DATA; INFORMATION; NITROGEN COMPOUNDS; NUMERICAL DATA; ORGANIC COMPOUNDS; PNICTIDES; RADICALS; REFRACTORY METAL COMPOUNDS; SYNTHESIS; TRANSITION ELEMENT COMPOUNDS; 400201* - Chemical & Physicochemical Properties

Citation Formats

Chan, D M.T., Chisholm, M H, Folting, K, Huffman, J C, and Marchant, N S. Trialkoxynitridomolybdenum compounds: (RO)/sub 3/Mo identical with N. Preparation, structures (R = t-Bu and i-Pr), and comparisons with a tungsten analogue (R = t-Bu). United States: N. p., 1986. Web. doi:10.1021/ic00243a023.
Chan, D M.T., Chisholm, M H, Folting, K, Huffman, J C, & Marchant, N S. Trialkoxynitridomolybdenum compounds: (RO)/sub 3/Mo identical with N. Preparation, structures (R = t-Bu and i-Pr), and comparisons with a tungsten analogue (R = t-Bu). United States. https://doi.org/10.1021/ic00243a023
Chan, D M.T., Chisholm, M H, Folting, K, Huffman, J C, and Marchant, N S. 1986. "Trialkoxynitridomolybdenum compounds: (RO)/sub 3/Mo identical with N. Preparation, structures (R = t-Bu and i-Pr), and comparisons with a tungsten analogue (R = t-Bu)". United States. https://doi.org/10.1021/ic00243a023.
@article{osti_6970928,
title = {Trialkoxynitridomolybdenum compounds: (RO)/sub 3/Mo identical with N. Preparation, structures (R = t-Bu and i-Pr), and comparisons with a tungsten analogue (R = t-Bu)},
author = {Chan, D M.T. and Chisholm, M H and Folting, K and Huffman, J C and Marchant, N S},
abstractNote = {The compound (t-BuO)/sub 3/Mo identical with N is formed in the reaction between Cl/sub 3/Mo identical with N and LiO-t-Bu (3 equiv) in THF and is obtained as a white crystalline compound by either sublimation (85/sup 0/C, 5 x 10/sup -3/ torr) or recrystallization from toluene. In the solid state the compound forms a linear polymer ((t-BuO)/sub 3/Mo identical with N) involving alternating short, 1.66 (1) A, and long, 2.86 (2) A, Mo-N bonds, corresponding formally to triple and weak dative bonds, respectively. In benzene solution, a cryoscopic molecular weight determination indicates the monomeric species is present. The solubilities of the compounds ((t-BuO)/sub 3/M identical with N) where M = Mo and W differ quite markedly, with the molybdenum compound being appreciably more soluble in aromatic solvents. It is suggested that this results from different M identical with N - M bonding along the infinite chain with the tungsten compound having a more basic or nucleophilic nitrogen atom. This suggestion finds support from MO calculations employing the Fenske-Hall method. The W identical with N distance is significantly longer (1.740 (15) A) and the W-N distance shorter (2.661 (15) A). Furthermore, the molybdenum and tungsten compounds differ in their reactivity toward alcohols, yielding, respectively, (RO)/sub 3/Mo identical with N and W(OR)/sub 6/ (R = i-Pr, neo-Pe, Et) and ammonia. These results are compared with other nitrido compounds of molybdenum and tungsten. Crystal data for (t-BuO)/sub 3/Mo identical with N is presented. 19 references, 3 figures, 4 tables.},
doi = {10.1021/ic00243a023},
url = {https://www.osti.gov/biblio/6970928}, journal = {Inorg. Chem.; (United States)},
number = ,
volume = 25:23,
place = {United States},
year = {Wed Nov 05 00:00:00 EST 1986},
month = {Wed Nov 05 00:00:00 EST 1986}
}