Three complexes which resulted from the C-N bond cleavage reactions of formamidinate anions, [ArNC(H)NAr](-), have been synthesized and structurally characterized. The reaction of N,N’-diphenylformamidinate, DPhF(-), with (Me(2)S)Cl2Ta(mu-Me(2)S)(mu-Cl)(2)TaCl2(SMe(2)) (abbreviated as Ta2Cl6(SMe(2))(3)) in the presence of Zn metal produces the CNPh-containing dinuclear compound (eta(2)-DPhF)(2)Ta(mu-NPh)(mu-eta(2)-CNPh)Ta(eta(2)-DPhF)(2) . C7H8, 1 . C7H8. By using DTolF(-) and Na/Hg as reducing agent, the isolated product is (eta(2)-DTolF)Ta(mu-NTol)(mu-eta(2)-CNTol)(mu-DTolF)(2)Ta(eta(2)-DTolF) . 1.5C(6)H(14), 2 . 1.5C(6)H(14), where DTolF(-) = N,N’-di(p-tolyl)formamidinate. Both 1 and 2 are isolated in low yields. There is a formal single bond between the tantalum atoms which are bonded to intact formamidinate ions as well as the two fragments which result from the cleavage of a formamidinate ligand, namely arylimido (NAr2-) and (CNAr). In the absence of a reducing agent, the reaction of LiDTolF and Ta2Cl6(SMe(2))(3) produces Cl-2(eta(2)-DTolF)Ta(mu-NTol)(mu-eta(2), eta(2)-HCNTol)Ta(eta(2)-DTolF)(2), 3, in high yield. In addition to the tolylimido group, a tolylformimidoyl fragment (HCNTol) binds to the tantalum atom through both carbon and nitrogen atoms in a eta(2),eta(2) mode. Because of this and the relatively long C-N bond distance (1.42(1) Angstrom), the ligand can be formulated as [HCNTol](3-). Thus the tantalum atoms in 3 have a formal oxidation state of +5, which precludes the presence of a metal-metal bond. Crystal data for 1 . C7H8 : monoclinic, I2/a, a = 19.437(2) Angstrom, b = 15.587(1) Angstrom, c = 20.401(1) Angstrom, and beta = 97.840(6)degrees. Crystal data for 2 . 1.5C(6)H(14) : triclinic, , a = 13.990(2) Angstrom, b = 15.841(1) Angstrom, c = 19.442(4) Angstrom, alpha = 98.98(1)degrees, beta = 104.07(1)degrees; gamma = 109.59(1)degrees. Crystal data for 3 : monoclinic, P2(1)/n, a = 17.962(3) Angstrom, b = 15.539(4) Angstrom, c = 19.973(3) Angstrom, beta = 90.126(7)degrees.