The half-sandwich tetra-tert-butylcarbazol-9-yl iodo complex [(tBu(4)Carb)Sm(m-I)(THF)(2)](2) (1) was synthesized by the salt metathesis reaction of tBu(4)CarbK and SmI2(THF)(2) in THF. Complex 1 along with metallic Cu was also isolated from the oxidation reaction of (tBu(4)Carb)(2)Sm by CuI. The formation of stable radical tBu(4)Carb(center dot) was detected in this non-conventional process, indicating preferential oxidation of anion tBu(4)Carb(-) vs. Sm-II. The treatment of 1 with two equivalents of dibenzo-18-crown-6 resulted in heterolytic dissocia-tion of a h 5-bond Sm-tBu(4)Carb and afforded an ionic compound [tBu(4)carb(-)][SmI(crown)(THF)(2)](+) (4). Alkylation of 1 with o-NMe2C6H4CH2K (1: 2 molar ratio) in THF allowed for the synthesis of half-sandwich SmII alkyl complex (tBu(4)Carb) SmCH2(o-NMe2C6H4CH2)(THF)(2) (5) in 55% yield. The amido complex (tBu(4)Carb) SmN(SiMe3)(2)(DME) (6) was obtained by the reaction of 1 with two molar equivalents of NaN(SiMe3)(2) in THF in 89% yield.