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首页> 外文期刊>Chemistry: A European journal >Rearrangement of a Transient Gold Vinylidene into Gold Carbenes
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Rearrangement of a Transient Gold Vinylidene into Gold Carbenes

机译：将瞬态金乙烯基重新排列成金碳酸盐

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摘要

The gold acetylide complex 20 endowed with a biaryl backbone provides opportunities for a study on the formation and fate of gold vinylidenes. Although the formyl group in 20 is not sufficiently electrophilic to get attacked by the acetylide in proximity, its activation with TBSOTf (TBSOTf=tert-butyldimethylsilyl trifluoromethanesulfonate) at low temperature triggered instantaneous formation of a gold vinylidene (21). This metastable species evolved into the cationic gold carbene complex 22 bearing a phenanthrene unit and a hydroxyl group at the aurated center; the recorded data suggest that this product might be better viewed as an acylgold species protonated by triflic acid. The use of [Me_3O·BF_4] as the activating agent led to formation of the analogous Fischer-type carbene 24, whereas replacement of gold by the [CpRu(PPh_3)_2]~+ fragment allowed the ruthenium vinylidene 27 to be isolated, which closely resembles the proposed gold intermediate 21. The starting gold complex 20, the derived products 22 and 24, as well as vinylidene 27 were characterized by X-ray diffraction.
机译：金乙酰乙酰络合物20赋予了骨架骨架，为金乙烯基的形成和命运提供了研究的机会。虽然20中的甲酰基在邻近乙酰乙酰乙酰乙酰酯中不充分电泳，但其在低温下用TBSOTF（TBSOTF =叔丁基二甲基甲酰基三氟甲磺酸盐）在低温下触发金乙烯基（21）的瞬时形成。这种亚稳态物种演化到亚苯乙烯单元和防腐中心的羟基含有亚膦族卡贝络合物22;记录的数据表明，该产品可以更好地观察为由三氟乙酸质子质原态的acylgold物种。使用[ME_3O·BF_4]作为激活剂导致形成类似的费 - 型卡宾酯24，而通过[CPRU（PPH_3）_2]〜+片段替换金，允许钌亚乙烯基27被隔离，密切类似于所提出的金中间体21.起始金复合物20，衍生的产物22和24以及偏二丙烯27的特征在于X射线衍射。

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