A general route to tungsten(VI) imido alkylidene bispyrrolide complexes via the extrusion of CO₂ from the reaction of one equivalent of an aryl isocyanate with WOCl₄ to form the corresponding imido complexes is reported. The otherwise required 2-fold excess of an aniline derivative in this reaction sequence is circumvented in the reaction of W(O)Cl₄ with Ar-NCO (Ar = 2,6-Me₂-C₆H₃, 2,6-ⁱPr₂-C₆H₃, 2,6-Cl₂-C₆H₃, 3,5-Me₂-C₆H₃) to W(NAr)Cl₄. In the subsequent steps, the scope of the synthesis of tungsten(VI) (NAr) alkylidene complexes via the isocyanate route, which was so far limited to Ar = 2,6-Me₂-C₆H₃ and 2,6-ⁱPr₂-C₆H₃, was extended to Ar = 2,6-Cl₂-C₆H₃ and 3,5-Me₂-C₆H₃. From those tungsten alkylidene complexes, the use of inexpensive and readily available reagents facilitates the synthesis of tungsten(VI) bispyrrolide complexes of the type W(NAr)(CHCMe₂Ph)(Pyr)₂(DME) and W(NAr)(CHCMe₂Ph)(Me₂Pyr)₂ (Ar = 2,6-Me₂-C₆H₃, 2,6-ⁱPr₂-C₆H₃, 2,6-Cl₂-C₆H₃, 3,5-Me₂-C₆H₃; Pyr = pyrrolide, Me₂Pyr = 2,5-dimethylpyrrolide), also avoiding the use of triflic acid. Thereby, both competitive yields with regard to previously published routes and high atom economy and thus cost-effectiveness are achieved. In addition, the peculiarities in the alkylation of complexes of the type W(NAr)(OtBu)₂Cl₂(THF) have been investigated and factors leading to undesired overalkylation are outlined.

中文翻译：

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异氰酸酯途径合成钨（VI）亚氨基钨亚烷基双吡咯化物配合物

据报道，通过从一当量的芳基异氰酸酯与WOCl _4的反应形成相应的酰亚胺基络合物的反应中挤出CO ₂，得到钨（VI）亚胺基亚烷基双吡咯化物络合物的一般路线。否则需要2倍过量的在该反应序列的苯胺衍生物是规避在W（O）Cl组成的反应₄用Ar-NCO（AR = 2,6-ME ₂ -C ₆ ħ ₃，2,6-^我镨₂ -C ₆ ħ ₃，2,6-CL ₂ -C ₆ ħ ₃，3,5--ME ₂ -C ₆ H ^ ₃）至W（N Ar）Cl ₄。在随后的步骤中，通过异氰酸酯途径合成钨（VI）（N Ar）亚烷基络合物的范围，到目前为止仅限于Ar = 2,6-Me ₂ -C ₆ H ₃和2,6-^我镨₂ -C ₆ ħ ₃，延伸到氩= 2,6-CL ₂ -C ₆ H ^ ₃和3,5--ME ₂ -C ₆ ħ ₃。从那些亚烷基钨配合物中，使用廉价易得的试剂有助于合成W（W）型双吡咯钨（VI）配合物Ñ AR）（CHCMe ₂ PH）（比利牛斯）₂（DME）和W（Ñ AR）（CHCMe ₂ PH）（ME ₂比利牛斯）₂（AR = 2,6-ME ₂ -C ₆ ħ ₃，2,6- -^我镨₂ -C ₆ ħ ₃，2,6-CL ₂ -C ₆ ħ ₃，3,5--ME ₂ -C ₆ H ^ ₃ ;比利=吡咯中，Me ₂吡咯= 2,5-二甲基吡咯化物），也避免使用三氟甲磺酸。从而，既获得了关于先前公开的路线的有竞争力的产量，又获得了高原子经济性，因此实现了成本效益。此外，在类型W（配合物的烷基化的特殊性Ñ AR）（O吨丁基）₂氯₂（THF）已被研究并导致不期望的因素overalkylation概述。