The chemistry of interactions of 2-(2,6-diisopropyl-phenylaminomethylene)indole ligand (1) with europium and ytterbium amides is described. Reaction of 2-(2,6-diisopropylphenylamino-methylene)indole 2-(2,6-i-Pr2C6H3NHCH2)C8H5NH (1) with europium amide [(Me3SO2N](3)Eu-III(mu-Cl)Li(THF)(3) afforded a novel europium(II) complex formulated as {[mu-eta(6):eta(1):eta(1)-2-(2,6-i-Pr2C6H3N=CH)C8H5N]Eu[2-(2,6-i-Pr2C6H3N=CH)C8H5N]}(2) (2), having a bridged indolyl ligand in the novel mu-eta(6):eta(1):eta(1) hapticities with the reduction of europium(III) to europium(1) and the oxidation of amino to imino group. Reaction of 2-(2,6-diisopropylphenyl-aminomethylene)indole 2-(2,6-i-Pr2C6H3NHCH2)C8H5NH (1) with ytterbium(III) amide [(Me3Si)(2)N](3)Yb-III(mu-Cl)Li(THF)(3) produced the only deprotonated ytterbium(III) complex formulated as [2-(2,6-i-Pr2C6H3NCH2)C8H5N]Yb[N(SiMe3)(2))(THF)(2) (3), having an hapticity indolyl ligand. Reaction of 2 with formamidine [(2,6-Me2C6H3)NCHNH(C6H3Me2-2,6)] produced {[mu-eta(3):eta(1):eta(1)-2-(2,6-i-Pr2C6H3N=CH)C8H5N]Eu[(2,6-Me2C6H3)NCHN(C6H3Me2-2,6)](THF)}(2) (4), which has a bridged indolyl ligand in the novel mu-eta(3):eta(1):eta(1) hapticities, whereas the reaction of 2 with the more sterically bulky formamidine [(2,6-i-Pr2C6H3)NCHNH(C(6)H(3)i-Pr-2-2,6)] afforded complex {[mu-eta(2):eta(1):eta(1)-2-(2,6-i-Pr2C6H3N=CH)C8H5N]Eu[(2,6-i-Pr2C6H3)N=CHN(C(6)H(3)i-Pr-2-2,6)](THF)}(2) (5), having the indolyl ligand in the novel mu-eta(2):eta(1):eta(1) hapticities. The results represent the first example of organometallic complexes having indolyl ligands in the novel mu-eta(6):eta(1):eta(1), mu-eta(3):eta(1):eta(1), and mu-eta(2):eta(1):eta(1) bonding modes with metal.