Syntheses, Structures, and Dynamic Behavior of Chiral Racemic Organoantimony and -bismuth Compounds RRSbCI, RRBiCI, and RRSbM [R = 2-(Me2NCH2)C6H4, R = CH(Me3Si)2, M = H, Li, Na]

RRʹSbCI (1) and RRʹBiCI (2) [R = 2-(Me2NCH2)C6H4, Rʹ = CH(Me3Si)2] form by the reaction of RʹEC (E - Sb, Bi) with RLi. The reaction of 1 with UAII and metalation with n-BuLi gives RRʹSbH (3) and RRʹSbLi-2THF (4) (THF = tetrahydrofuran). Transmetalation of 4 with sodium tert-butoxide in the presence of TMEDA (TMEDA = tetramethylethylenediamine) leads to RRʹSbNa-TMEDA (5). Structural analyses by H NMR in CeDe, C6D5CD3, or (CD3)2 SO with a variation of the temperature (1, 2, 4, and 5) and by single-crystal X-ray diffraction (1, 2, 4, and 5) revealed the intramolecular coordination of the pendant Me2N group on the pnicogen centers in 1 and 2 and on Li or Na in 4 or 5. The variable-temperature H NMR spectra of the hydride 3 in C6D6, C6D5CD3, or (CD3)2 SO show that the pyramidal configuration on antimony is stable up to 100 °C, whereas inversion at the nitrogen is not prevented by internal coordination even at -80 °C. The crystals of 1, 2,4, and 5 consist of discrete molecules with the 8b and Bi atoms in an approximately -trigonal-bipyramidal environment in the cases of land 2 and in a