多才多艺的双铋烯：利用单个或两个铋中心实现双C(sp)─I键活化
Multi-Talented Bismuthinidenes: Double C(sp)─I Bond Activation Using Single or Two Bi Centers.
作者信息
Novák Pavel, Hejda Martin, Jambor Roman, Růžička Aleš, Gagnon Alexandre, Dostál Libor
机构信息
Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, Pardubice, CZ-532 10, Czech Republic.
Université du Québec à Montréal (UQAM), Québec, Montréal, H3C 3P8, Canada.
出版信息
Chemistry. 2025 Jun 12;31(33):e202500620. doi: 10.1002/chem.202500620. Epub 2025 May 15.
The reaction of [2,6-(DippN = CH)CH]Bi (1Dipp, Dipp = 2,6-iPrCH) with CHI proceeded via double C─I bond activation yielding [2,6-(DippN = CH)CH]Bi(μ-(Bi,N)─CH)I (3). By contrast, the reaction of 1Dipp with 1,2-diiodoethane provided [2,6-(DippN═CH)CH]BiI (1DippI) and ethene. The tert-butyl analogue [2,6-(tBuN═CH)CH]Bi (1tBu) reacted with CHClX to give [2,6-(tBuN═CH)CH]Bi(CHCl)X (X═I (4) or Cl (5)). Further, its reactivity with CHI was sensitive towards the stoichiometry since using a 1:1 ratio gave a mixture of dinuclear complex {[2,6-(tBuN═CH)CH]Bi(I)}(μ-(Bi,Bi)─CH) (6) and [2,6-(tBuN═CH)CH]Bi(CHI)I (7). The reaction could be shifted in favor of 7 using an excess of CHI, but with 0.45 eq. of CHI compound 6, as a product of double C─I bond activation mediated by two Bi atoms was isolated as the main product.
[2,6-(二异丙基苯基氮=CH)CH]Bi（1Dipp，二异丙基苯基=2,6-二异丙基苯基）与CHI的反应通过双C─I键活化进行，生成[2,6-(二异丙基苯基氮=CH)CH]Bi(μ-(Bi,N)─CH)I（3）。相比之下，1Dipp与1,2-二碘乙烷的反应生成了[2,6-(二异丙基苯基氮═CH)CH]BiI（1DippI）和乙烯。叔丁基类似物[2,6-(叔丁基氮═CH)CH]Bi（1tBu）与CHClX反应生成[2,6-(叔丁基氮═CH)CH]Bi(CHCl)X（X═I（4）或Cl（5））。此外，它与CHI的反应对化学计量比敏感，因为使用1:1的比例会得到双核配合物{[2,6-(叔丁基氮═CH)CH]Bi(I)}(μ-(Bi,Bi)─CH)（6）和[2,6-(叔丁基氮═CH)CH]Bi(CHI)I（7）的混合物。使用过量的CHI可使反应偏向于生成7，但使用0.45当量的CHI时，由两个Bi原子介导的双C─I键活化产物6被分离为主要产物。
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