| Sumario: | The cycloheptatrienyl-cyclopentadienyl sandwich complex [η-CH)Ti(η-CH)) (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 CIPPh2 afforded the corresponding troticenyl-phosphanes [(η-CHPPh)Ti(η-CHPPh)] (1), [(η-CHPPh)Ti(η-CH)] (2), or [(η-CH)Ti(η-CHPPh)] (3). The use of nBuLi/N,W,W,W',N'-pentamethyldiethylenetriamine (pmdta) allowed us to isolate the lithium complexes [(η-CHLi)Ti(η-CHLi)]·pmdta (4) and [(η-CH)Ti(η-CHLi)]-pmdta (5), which were structurally characterized by X-ray diffraction analyses. Reaction of the monophosphane 3 with Mo(CO) and [(tht)AuCI] (tht = tetrahydrothiophene) afforded the heterobimetallic complexes [(3)Mo(CO)] (6) and [(3)AuCI] (7) and also the trimetallic species [(3)AuCl] (8). The reaction of trans-[PtCI(SEt)] with the diphosphane 1 led to the formation of cis-[(1)PtCI] (9), whereas the complexes trans-[(2)PtCI] (10) and trans-[(3)PtCI] (11) were isolated by reaction of two equivalents of the monophosphanes 2 and 3 with trans-[PtCI(SEt)]. The X-ray crystal structures of 6-11 are also reported.
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