Diverse Reactivity of bis(Silylene) and bis(Germylene) [LE−EL (E=Si and Ge: L=PhC(NtBu)2)] in the Oxidative Activation of C−F Bond: Si−Si Bond is Retained While the Ge−Ge Bond Is Cleaved

Abstract

AbstractHerein we report the reactions of 3,4,5,6‐tetrafluoroterephthalonitrile (1) with bis(silylene) and bis(germylene) LE−EL [E=Si (2) and Ge(3): L=PhC(NtBu)2)]. The reaction of LSi−SiL (L=PhC(NtBu)2) (2) with two equivalents of 1 resulted in an unprecedented oxidative addition of a C−F bond of 1 leading to disilicon(III) fluoride {L(4‐C8F3N)FSi−SiF(4‐C8F3N)L}(4), wherein the Si−Si single bond was retained. In contrast, the reaction of LGe−GeL (L=PhC(NtBu)2) (3) with one equivalent of 1 resulted in the oxidative cleavage of Ge−Ge bond leading to L(4‐C8F3N2)Ge (5) and LGeF (6). All three compounds (4–6) were characterized by NMR spectroscopy, EI‐MS spectrometry, and elemental analysis. X‐ray single‐crystal structure determination of compound 4 unequivocally established that the SiIII−SiIII bond remains uncleaved.