Trialkoxynitridomolybdenum compounds: (RO)3Mo.ident.N. Preparation, structures (R = tert-Bu and iso-Pr), and comparisons with a tungsten analog (R = tert-Bu)
Trialkoxynitridomolybdenum compounds: (RO)3Mo.ident.N. Preparation, structures (R = tert-Bu and iso-Pr), and comparisons with a tungsten analog (R = tert-Bu)
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三烷氧基氮化钼化合物：(RO)3Mo.ident.N。
DOI：
10.1021/ic00243a023
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发表时间：
1986
期刊：
影响因子：
--
通讯作者：
N. Marchant
中科院分区：
文献类型：
--
作者：
D. M. Chan;M. Chisholm;K. Folting;J. Huffman;N. Marchant
与N相同的Cl/sub -3/ Mo与LiO-t-Bu（3当量）在THF中反应生成与N相同的化合物(t-BuO)/sub -3/ Mo，通过升华（85/sup 0/C, 5 × 10/sup -3/ torr）或甲苯重结晶得到白色结晶化合物。在固体状态下，该化合物形成一种线性聚合物（(t-BuO)/sub 3/Mo，与N相同），其短键（1.66 (1)a）和长键（2.86 (2)a） Mo-N交替存在，形式上分别对应于三键和弱键。在苯溶液中，低温分子量测定表明存在单体。当M = Mo和W时，化合物（(t-BuO)/sub - 3/M与N相同）的溶解度差异很大，其中钼化合物在芳香溶剂中的溶解度明显提高。认为这是由于不同的M与无限链上的N - M键相同，而钨化合物具有更碱性或亲核的氮原子。这一建议得到了采用Fenske-Hall方法的MO计算的支持。W与N相同的距离较长（1.740 (15)A）， W-N距离较短（2.661 (15)A）。此外，钼和钨化合物对更多»醇的反应性不同，分别生成(RO)/sub - 3/Mo与N相同，W(OR)/sub - 6/ (R = i-Pr, neo-Pe, Et)和氨。这些结果与其他钼和钨的氮化化合物进行了比较。给出了与N相同的(t-BuO)/sub - 3/Mo的晶体数据。参考文献19篇，图3张，表4张。«少
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