Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104, United States.
J Am Chem Soc. 2015 Jul 22;137(28):8884-7. doi: 10.1021/jacs.5b04853. Epub 2015 Jul 14.
The Ti(III) azido complex (PN)2Ti(N3) (PN(-) = (N-(2-(diisopropylphosphino)-4-methylphenyl)-2,4,6-trimethylanilide), can be reduced with KC8 to afford the nitride salt [μ2-K(OEt2)]2[(PN)2Ti≡N]2 in excellent yield. While treatment of the dimer with 18-crown-6 yields a mononuclear nitride, complete encapsulation of the alkali metal with cryptand provides the terminally bound nitride as a discrete salt [K(2,2,2-Kryptofix)][(PN)2Ti≡N]. All complexes reported here have been structurally confirmed and also spectroscopically, and the Ti-Nnitride bonding has been probed theoretically via DFT-based methods.
Ti(III)叠氮配合物(PN)2Ti(N3)(PN(-)=(N-(2-(二异丙基膦基)-4-甲基苯基)-2,4,6-三甲基苯胺)，可以用 KC8 还原得到氮化物盐[μ2-K(OEt2)]2[(PN)2Ti≡N]2，产率很高。而二聚体与 18-冠-6 反应则得到单核氮化物，用 cryptand 完全包裹碱金属则得到末端键合的氮化物作为离散盐[K(2,2,2-Kryptofix)][(PN)2Ti≡N]。这里报道的所有配合物都经过了结构确证和光谱分析，并且通过基于 DFT 的方法从理论上探测了 Ti-N 氮化物键。
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