A series of hydrotris(indazolyl)borates containing diverse substituents on the indazole ring and representing two types of regiochemistries have been synthesized. Indazoles with a 7-alkyl substituent or a 6,7-fused benzo ring formed ligands with boron bonded to the less hindered N-2 (=Tp(3Bo)), while those with alkyl or aryl substituents in any other position yielded ligands with boron bonded to the more hindered N-1 (=Tp(4Bo)), thus being the first example of homoscorpionates with 4,5-substituents. Octahedral home-and heteroleptic complexes of Co, Fe, and Zn have been prepared and characterized, as well as complexes of the types [M(L)(NCS)], [Mo(L)(CO)(2)(eta(3)-CH2CMeCH2)], [Rh(L)(COD)], and [Rh(L)(CO)(2)]. X-ray crystallography provided structures of the complexes [Rh(HB{3-methylindazol-1-yl}(3))(COD)], 1 (space group P2(1)/n; a = 11.766(2), b = 16.189(2), c = 15.149(2) Angstrom; beta = 92.51(1)degrees; Z = 4; R = 0.0306 for 4318 independent reflections), [Co(HB{7-methylinazol-2-yl}(3))(HB{3-neopentylpyrazol-1-yl}(3))], 2 (space group P (1) over bar; a = 13.368(4), b = 13.652(4), c = 16.203(9) Angstrom; alpha = 73.73(4), beta = 71.26(3), gamma = 63.54(2)degrees; Z = 2; R = 0.0761 for 7721 independent reflections), and [Co(hydrotris{3-methyl-2H-benz[g]indazol-2-yl}borate)(hydrotris{3-neopentylpyrazol-1-yl}borate)]. C6H5CN, 3 (space group P (1) over bar; a = 13.216(6), b = 13.706(4), c = 17.881(6) Angstrom; alpha = 73.79(2), beta = 86.71(3), gamma = 85.61(3)degrees; Z = 2; R = 0.1138 for 6698 independent reflections).