The synthesis and reactivity of the heavier group 13 phosphaketene complexes (2,6-Mes2C6H3)2EPCO (1, E = Ga; 2, E = In) were reported. The reaction of 1 and 2 with 1,2,3,4-tetramethylimidazolin-2-ylidene,...
The newly prepared and fully characterized stibenium and bismuthenium ions [RindMesE]+ (E=Sb, Bi; Rind=dispiro[fluorene‐9,3′‐(1′,1′,7′,7′‐tetramethyl‐s‐hydrindacen‐4′‐yl)‐5′,9′′‐fluorene) were rigorously compared to the previously communicated phosphenium and arsenium ions (E=P, As) as well as the bis(m‐terphenyl) pnictogenium ions [(2,6‐Mes2C6H3)2E]+ (E=Sb, Bi). It is demonstrated that the choice of the aryl substituents dramatically effects the molecular structures (e. g. the primary E−C bond lengths) and the electronic structures (e. g. the energy of the LUMOs).
The kinetically stabilized group 14 cations [RindEMe2][B(C6F5)4] (E = Si, Sn, Pb) were prepared and fully characterized (Rind = dispiro[fluorene-9,3'-(1',1',7',7'-tetramethyl-s-hydrindacen-4'-yl)-5',9''-fluorene). The deshielded heteronuclear NMR chemical shifts (δ(29Si) = 160.4, δ(119Sn)...
Kinetic stabilization using bulky m‐terphenyl substituents is the key to the isolation of the diarylantimony and diarylbismuth phosphaethynolates (2,6‐Mes2C6H3)2EPCO and the related N‐heterocyclic carbene complexes (2,6‐Mes2C6H3)2EP(O)C(IMe4) (E=Sb, Bi; IMe4=1,3,4,5‐tetramethylimidazol‐2‐ylidene), which have been fully characterized crystallographically and spectroscopically. The experimental characterization was augmented by a DFT based real space bond indicator analysis of the electron density, including AIM, NCI, and ELI‐D methods.
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