Probing the Limits of Oxidative Addition of C(sp<sup>3</sup>)–X Bonds toward Selected <i>N,C,N</i>-Chelated Bismuth(I) Compounds
Martin Hejda, Robert Jirásko, Aleš Růžička, Roman Jambor, Libor Dostál
Abstract
The reactivity of two N,C,N-chelated bismuthinidenes, that is, [2,6-(tBuN═CH)2C6H3]Bi (1) and its metastable analogue [2,6-(Me2NCH2)2C6H3]Bi (2), toward organic substrates containing C(sp3)–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); 1H, 13C, and 19F NMR spectroscopy; and single-crystal X-ray diffraction analysis.