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

Abstract

Abstract Herein 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(N t Bu) 2 )]. The reaction of LSi−SiL (L=PhC(N t Bu) 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‐C 8 F 3 N)FSi−SiF(4‐C 8 F 3 N)L}( 4 ), wherein the Si−Si single bond was retained. In contrast, the reaction of LGe−GeL (L=PhC(N t Bu) 2 ) ( 3 ) with one equivalent of 1 resulted in the oxidative cleavage of Ge−Ge bond leading to L(4‐C 8 F 3 N 2 )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 Si III −Si III bond remains uncleaved.