The compounds [CpTi(SCH2CH2S)2Na]n and [CpTi(SCH2CH2CH2S)2Na]n have been used as precursors to heterometallic compounds. Reaction with [Cu(NCMe)4]BF4 gives insoluble compounds formulated as [CpTi(SCH2CH2S)2Cu]n (1) and [CpTi(SCH2CH2CH2S)2)Cu]n (2), respectively. Compound 1 is also formed in the reaction of [CpTi(SCH2CH2S)Cl]2 With [Cu(NCMe)4]BF4. The Rh(I) derivative [CpTi(SCH2CH2CH2S)2Rh]n (3) has been synthesized from the reaction of [CpTi(SCH2CH2CH2S)2Na]n and [(C2H4)2RhCl]2. Compounds 1 and 2 react with PMe3 to give CpTi(SCH2CH2S)2CuPMe3 (4) and CpTi(SCH2CH2CH2S)2CuPMe3 (5), respectively. In compound 4 the Ti coordination sphere is best described as a pseudo-four-legged piano stool while three sulfur atoms bridge to the CuPMe3 fragment completing the pseudotetrahedral coordination sphere of Cu. Reaction of 1 with bis(dimethylphosphino)ethane (DMPE) leads to the formation of the salt [CpTi(SCH2CH2S)2] [Cu(DMPE)2] (6), in which the cation and anion have no close contacts. Addition of 1 equiv of NBD to a suspension of 4 generates [CpTi(SCH2CH2CH2S)2]Rh(NBD) (7). Compound 7 is also prepared by reaction of CpTi(SCH2CH2CH2S)Cl with [(NBD)RhCl]2 or [(NBD)2Rh]BF4. In a manner similar to observations in 3, three of the sulfur atoms bound to Ti bridge to the pseudotrigonal bipyramidal Rh center in 7. This compound is not stable in solution, decomposing to the Ti(III) product [CpTi(SCH2CH2CH2S)2][Rh(NBD)]2 (8). In this case,the Rh centers adopt pseudo square planar geometries with two bridging sulfur atoms with the NBD fragment completing the coordination sphere. These results are presented, and the implications regarding the nature of these heterobimetallic complexes is considered. Structural data are presented for the compounds 4, 6, 7, and 8. Complex 4 crystallizes in the triclinic space group P1BAR with a = 9.458(1) angstrom, b = 11.297(2) angstrom, c = 9,244(1) angstrom, alpha = 93.96(1)degrees, beta = 103.63(1)degrees, gamma = 106.41(1)degrees, V = 911.0(3) angstrom3, and Z = 2. Compound 6 crystallizes in the monoclinic space group P2(1)/n with a = 12.453(9) angstrom, b = 19.002(8) angstrom, c = 14.231(5) angstrom, beta = 105.71(3)degrees, V = 3245(2) angstrom3, and Z = 4. Compound 7 crystallizes in the monoclinic space group P2(1)/n with a = 9.182(7) angstrom, b = 12.222(3) angstrom, c = 17.557(4) angstrom, beta = 91.83(4)degrees, V = 1958(1) angstrom3, and Z = 4. Compound 8 crystallizes in the tetragonal space group P4(1)2(1)2 with a = 11.346(5) angstrom, c = 23.531(8) angstrom, V = 3029(1) angstrom3, and Z = 4.