Novák Pavel, Hejda Martin, Jambor Roman, Růžička Aleš, Gagnon Alexandre, Dostál Libor
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.
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。
