The stereochemistry of the chelate rings of a number of rhodium aminophosphine complexes is studied by NMR spectroscopy. The similarity in the variable-temperature behavior for the different compounds is consistent with them having in common highly preferred chelate ring conformations. The six-membered metallacycle of coordinated (R)-P*N (P*N = o-diphenylphosphino-alpha-methyl-N,N-dimethylbenzylamine) adopts a delta conformation in the solid state. NMR experiments indicate that this conformation is strongly favored in solution as well. The preferred sense of helicity is imposed by the absolute configuration of the stereogenic carbon atom on the ligand, which exerts an important steric control. The complex [Rh(TFB){(C6H4CHMeNMe2)(2)P(C6H4CHMeNHMe2)}](BF4)(2)(H2OMe2CO)-H-.-Me-. crystallizes in the monoclinic space group P2(1) with a = 12.0548(11) Angstrom, b = 16.139(2) Angstrom, c = 12.1804(10) Angstrom, beta = 100.742(9)degrees, Z = 4.