2,6‐Diisopropylphenyl substituted Bismuth Halide and Interpnictogen Compounds

Abstract Herein, we report about the preparation of several new 2,6‐di iso propylphenyl (Dipp) substituted (halido‐) bismuthanes, namely, Dipp 3 Bi ( 1 ) and compounds of the form DippBiX 2 (X=Cl, Br, I; 2 – 4 ). The compounds 2 – 4 show a variety of structural motifs in their solid state structures. Reactivity of 2 towards the nucleophiles LiNMe 2 and MeLi was examined, where mostly scrambling reactions with a preference for two Dipp substituents at bismuth were observed. Therefore, the compounds Dipp 2 BiNMe 2 ( 5 ) and Dipp 2 BiMe ( 6 ) are the main products of these reactions. Moreover, new interpnictogen compounds with Bi−N, ‐P, and ‐Sb single bonds were prepared. Compound 5 was successfully used as precursor for the preparation of Dipp 2 BiNH t Bu ( 7 ) and Dipp 2 BiSbMes 2 ( 8 ), one of very few isolated compounds with a Bi‐Sb single bond. Moreover, bismuthanyl phosphanes bearing functional groups (Dipp 2 BiP t Bu(SiMe 3 ) ( 9 ), Dipp 2 BiPH t Bu ( 10 )) have been prepared. Compound 10 is the first isolated secondary phosphane with a bismuthanyl substituent. All isolated compounds were analyzed via IR and NMR spectroscopy, mass spectrometry, elemental analysis and single crystal X ray diffraction.