Szlosek Robert, Seidl Michael, Balázs Gábor, Scheer Manfred
Institut für Anorganische Chemie, Universität Regensburg, 93053, Regensburg, Germany.
Chemistry. 2023 Sep 21;29(53):e202301752. doi: 10.1002/chem.202301752. Epub 2023 Aug 16.
A general pathway towards NHC (NHC=N-heterocyclic carbene)-stabilized galliummonotriflates NHC ⋅ GaH (OTf) (NHC=IDipp, 1 a; IPr Me , 1 b; IMes, 1 c; IDipp=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene, IPr Me =1,3-bis-(diisopropyl)-4,5-dimethyl-imidazolin-2-ylidene, IMes=1,3-bis(2,4,6-trimethylphenyl)-imidazolin-2-ylidene) is reported. Quantum chemical calculations give detailed insight into the underlying reaction pathway. The obtained NHC ⋅ GaH (OTf) compounds were employed in reactions with donor-stabilized pnictogenylboranes to synthesize the elusive cationic parent 13/15/13 chain compounds [IDipp ⋅ GaH ER E'H ⋅ D][OTf] (3 a: D=IDipp, E=P, E'=B, R=H; 3 b: D=NMe , E=P, E'=B, R=H, 3 c: D=NMe , E=P, E'=B, R=Ph, 3 d: D=IDipp, E=P, E'=Ga, R=H). Supporting computational studies highlight the electronic features of the products.
报道了一条通向NHC（NHC = N-杂环卡宾）稳定的三氟甲磺酸镓NHC⋅GaH(OTf)（NHC = IDipp，1a；IPrMe，1b；IMes，1c；IDipp = 1,3-双(2,6-二异丙基苯基)-咪唑啉-2-亚基，IPrMe = 1,3-双(二异丙基)-4,5-二甲基-咪唑啉-2-亚基，IMes = 1,3-双(2,4,6-三甲基苯基)-咪唑啉-2-亚基）的通用途径。量子化学计算深入洞察了潜在的反应途径。所得到的NHC⋅GaH(OTf)化合物用于与供体稳定的氮族元素硼烷反应，以合成难以捉摸的阳离子母体13/15/13链化合物[IDipp⋅GaHER E'H ⋅D][OTf]（3a：D = IDipp，E = P，E' = B，R = H；3b：D = NMe，E = P，E' = B，R = H，3c：D = NMe，E = P，E' = B，R = Ph，3d：D = IDipp，E = P，E' = Ga，R = H）。辅助计算研究突出了产物的电子特征。
