A series of complexes of the type Tp’Rh(CNCH2CMe3)(R)Cl, where R = CH3, CD3, n-propyl, isopropyl, cyclopropyl, and vinyl and Tp’ = tris(3,5-dimethylpyrazolyl)borate have been synthesized and fully characterized. The complexes are prepared by reaction of the corresponding Grignard reagent with Tp’Rh(CNCH2CMe3)Cl-2, which in turn is synthesized from Tp’Rh(NCCH3)Cl-2. The complex Tp’Rh(CNCH2CMe3)(isopropyl)Cl crystallizes in orthorhombic space group Pbcn (No. 60) with a = 27.8224(1) Angstrom, b = 14.2541(2) Angstrom, c = 14.5549(2) Angstrom, Z = 8, and V = 5772.23(9) Angstrom(3). The complex Tp’Rh(CNCH2CMe3)(cyclopropyl)Cl crystallizes in monoclinic space group P2(1)/c (No. 14) with a = 9.573(2) Angstrom, b = 18.933(3) Angstrom, c = 17.873(14) Angstrom, beta = 103.70(4)degrees, Z = 4, and V = 3147(3) Angstrom(3). The complex Tp’Rh(PMe3)Cl-2 crystallizes in monoclinic space group P2(1)/n (No. 14) with a = 10.9384(6) Angstrom, b = 17.3111(9) Angstrom, c = 13.5132(7) Angstrom, beta = 111.536(1)degrees, Z = 4, and V = 2378.5(2) Angstrom(3).