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)

Journal Article · Wed Nov 05 00:00:00 EST 1986 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00243a023· OSTI ID:6970928

Chan, D M.T.; Chisholm, M H; Folting, K; Huffman, J C; Marchant, N S

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.

• Research Organization: E.I. du Pont de Nemours and Co., Inc., Wilmington, DE
• OSTI ID: 6970928
• Journal Information: Inorg. Chem.; (United States), Vol. 25:23
• Country of Publication: United States
• Language: English

Related Subjects

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