Probing the Limits of Oxidative Addition of C(sp3)-X Bonds toward Selected N,C,N-Chelated Bismuth(I) Compounds

The reactivity of two N,C,N-chelated bismuthinidenes, that is, [2,6- (tBuN=CH)(2)C6H3]Bi (1) and its metastable analogue [2,6-(Me2NCH2)(2)C6H3]Bi (2), toward organic substrates containing C(sp(3))-X bond (where X = I or OTf) is reported. The aim of this study is to prove the potential of the Bi(I) center in 1 and 2 to participate in an oxidative addition toward C-X bonds under formation of corresponding trivalent bismuth compounds. The influence of the substrate is examined; thus, simple primary alkyls (including fluorinated ones) as well as more branched substrates are considered to find the limits of these reactions and recognize the differences in the reactivity between 1 and 2. All products were characterized by means of high-resolution electrospray ionization mass spectrometry (ESI-MS); H-1, C-13, and F-19 NMR spectroscopy; and single-crystal X-ray diffraction analysis.