Reactivity Studies of (tBu3SiNH)(tBu3SiN鈺?2WH Including Anionic Derivatives Featuring the Tris-tri-tert-butylsilylimide Tungsten Core

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• 作者：Daniel F. Schafer ; II ; Peter T. Wolczanski ; Emil B. Lobkovsky
• 刊名：Organometallics
• 出版年：2011
• 出版时间：December 26, 2011
• 年：2011
• 卷：30
• 期：24
• 页码：6539-6561
• 全文大小：1197K
• 年卷期：v.30,no.24(December 26, 2011)
• ISSN：1520-6041

文摘

Treatment of (^tBu₃SiNH)(^tBu₃SiN鈺?₂WH (1-H) with CX₄ (X = Cl, Br, I) afforded (^tBu₃SiNH)(^tBu₃SiN鈺?₂WX (1-X, X = Cl, Br, I), but metatheses of 1-X with R^{鈥?/sup> equivalents gave mixed results. With MeLi, (tBu₃SiNH)(tBu₃SiN鈺?₂WR (1-R, R = CH₃) was produced, but ArLi gave 1-Ar along with [(tBu₃SiN鈺?₃WAr]Li (2-Li-Ar) and [(tBu₃SiN鈺?₃WH]M (2-M-H, M = Li). Alkylation attempts with BnK and 1-X cause deprotonation (X = Cl) to provide [(tBu₃SiN鈺?₃WX]M (2-M-X, M = K, X = Cl) and apparent electron transfer when X = I to give 1-Bn, 2-K-H, and bibenzyl. Two equivalents of tBuLi and 1-Cl afforded 2-Li-H via deprotonation of 1-H and byproducts likely derived from electron transfer. Exposure of 1-H to C₂H₄, C₃H₆, methylenecyclopentane, butadiene, propyne, HCCtBu, p-tolunitrile, and tert-butylisocyanide gave insertion products 1-R (R = Et, nPr, CH₂cPe, E-CH₂CH鈺怌HMe, CH鈺怌HMe, CH鈺怌HtBu), 1-N鈺怌Htol, and 1-CH鈺怤tBu, respectively. Thermolysis of 1-CH鈺怤tBu gave the cyanide complex 1-CN. 1-H and 1-Me resisted dihydrogen and methane elimination in nondonor solvents at 200 掳C, but in pyridine, 1-H lost H₂ in a second-order process to give (tBu₃SiN鈺?₃Wpy (螖G掳_414K = 4.5 kcal/mol). Thermolysis of 2-py under D₂ in C₆D₆ provided 伪-deuterated py. 2-M-H (M = Li, Na, K) and 2-K-R (R = Me, Et, nPr) were generated by deprotonation of 1-H and 1-R, respectively, and various 1-M-X were synthesized similarly and via exposure of 1-Li-H to alkyl halides. Treatment of 2-Li-H with CH₃I provided 2-Li-I, but byproducts 1-CH₃ and 1-I suggested the potential intermediacy of a methane complex. X-ray crystal structures of 2-py, 2-H-K(OEt₂)₃, 2-H-K(crypt-2.2.2), the dimer [2-H]₂(渭-K)₂ (i.e., 2-K-H), and the trimer [2-I]₃(渭-K)₃ (i.e., 2-K-I) revealed similar tris-imido cores. Discussion of the general reactivity of 1-H, structural features, and plausible mechanisms of 2-py formation are included.}