The cycloheptatrienyl-cyclopentadienyl sandwich complex [(eta(7)-C7H7)Ti(eta(5)-C5H5)] (troticene) can be dilithiated (once at each ring) or selectively monolithiated, either at the seven- or five-membered ring, depending on the reaction conditions. Treatment of the resulting lithiotroticenes with ClPPh2 afforded the corresponding troticenyl-phosphanes [(eta(7)-C7H6PPh2)Ti(eta(5)-C5H4PPh2)] (1), [(eta(7)-C7H6PPh2)Ti (eta(5)-C5H5)] (2), or [(eta(7)-C7H7)Ti(eta(5)-C5H4PPh2)] (3). The use of nBuLi/N,N',N',N'-pentamethyldiethylenetriamine (pmdta) allowed us to isolate the lithium complexes [(eta(7)-C7H6Li)Ti(eta(5)-C5H4Li)]center dot pmdta (4) and [(eta(7)-C7H7)Ti(eta(5)-C5H4Li)]center dot pmdta (5), which were structurally characterized by X-ray diffraction analyses. Reaction of the monophosphane 3 with MO(CO)(6) and [(tht)AuCl] (tht = tetrahydrothiophene) afforded the heterobimetallic complexes [(3)Mo(CO)(5)] (6) and [(3)AuCl) (7) and also the trimetallic species [(3)(2)AuCl] (8). The reaction of trans-[PtCl2(SEt2)(2)] with the diphosphane 1 led to the formation of cis-[(1)PtCl2] (9), whereas the complexes trans-[(2)(2)PtCl2] (10) and trans-[(3)(2)PtCl2] (11) were isolated by reaction of two equivalents of the monophosphanes 2 and 3 with trans-[PtCl2(SEt2)(2)]. The X-ray crystal structures of 6-11 are also reported.