RR'SbCl (1) and RR'BiCl (2) [R = 2-(Me2NCH2)C6H4, R' = CH(Me3Si)(2)] form by the reaction of R'ECl2 (E = Sb, Bi) with RLi. The reaction of 1 with LiAlH4 and metalation with n-BuLi gives RR'SbH (3) and RR'SbLi.2THF (4) (THF = tetrahydrofuran). Transmetalation of 4 with sodium tert-butoxide in the presence of TMEDA (TMEDA = tetramethylethylenediamine) leads to RR'SbNa.TMEDA (5). Structural analyses by H-1 NMR in C6D6, 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 1H NMR spectra of the hydride 3 in CA, C6D5CD3, or (CD3)(2)SO show that the pyramidal configuration on antimony is stable up to 100 degreesC, whereas inversion at the nitrogen is not prevented by internal coordination even at -80 degreesC. The crystals of 1, 2, 4, and 5 consist of discrete molecules with the Sb and Bi atoms in an approximately Psi-trigonal-bipyramidal environment in the cases of 1 and 2 and in a pyramidal environment in the cases of 4 and 5. Crystal data for 1: triclinic, space group P $(1) over bar $, a = 7.243(4) Angstrom, b = 10.373(3) Angstrom, c = 15.396(5) Angstrom, alpha = 79.88degrees, beta = 78.27degrees, gamma = 71.480(10)degrees, V = 1066.2(7) Angstrom(3), Z = 2, R = 0.0614. 2: monoclinic, space group P2(1)/n, a = 10.665(2) Angstrom, b = 14.241(2) Angstrom, c = 14.058(2) Angstrom, beta = 90.100(10)degrees, V = 2135.1(6) Angstrom(3), Z = 4, R = 0.049. 4: monoclinic, space group P2(1)/n, a = 11.552(2) Angstrom, b = 16.518(3) Angstrom, c = 15.971(5) Angstrom, beta = 96.11(2)degrees, V = 3030.2(12) Angstrom(3), Z = 4, R = 0.0595. 5: monoclinic, space group P2(1)/n, a = 9.797(2) Angstrom, b 24.991(5) Angstrom, c = 14.348(3) Angstrom, beta = 94.98(3)degrees, V = 3499.66(12) Angstrom(3), Z = 4, R = 0.0571. The dissociation of the intramolecular N-pnicogen bond and inversion at the nitrogen occurs when solutions of 1 or 2 in C6D6 or C6D5CD3 are heated above 25 or 30degrees C. 1 and 3-5 are stable with respect to inversion of the configuration at the antimony in CA, C6D5CD3, or (CD3)(2)SO up to 160degrees C. Bismuth inversion, probably via the edge mechanism, is observed in solutions of 2 in (CD3)(2)SO at 45 degreesC but not in C6D5CD3 below 125 degreesC.