Synthesis and reactivity of boron-, silicon-, and tin-bridged ansa-cyclopentadienyl-cycloheptatrienyl titanium complexes (troticenophanes).

A novel one-pot method was developed for the preparation of [Ti(η(5)-C(5)H(5))(η(7)-C(7)H(7))] (troticene, 1) by reaction of sodium cyclopentadienide (NaCp) with [TiCl(4)(thf)(2)], followed by reduction of the intermediate [(η(5)-C(5)H(5))(2)TiCl(2)] with magnesium in the presence of cycloheptatriene (C(7)H(8)). The [n]troticenophanes 3 (n=1), 4, 8, 10 (n=2), and 11 (n=3) were synthesized by salt elimination reactions between dilithiated troticene, [Ti(η(5)-C(5)H(4)Li)(η(7)-C(7)H(6)Li)]⋅pmdta (2) (pmdta = N,N',N',N'',N''-pentamethyldiethylenetriamine), and the appropriate organoelement dichlorides Cl(2)Sn(Mes)(2) (Mes = 2,4,6-trimethylphenyl), Cl(2)Sn(2)(tBu)(4), Cl(2)B(2)(NMe(2))(2), Cl(2)Si(2)Me(4), and (ClSiMe(2))(2)CH(2), respectively. Their structural characterization was carried out by single-crystal X-ray diffraction and multinuclear NMR spectroscopy. The stanna[1]- and stanna[2]troticenophanes 3 and 4 represent the first heteroleptic sandwich complexes bearing Sn atoms in the ansa bridge. The reaction of 3 with [Pt(PEt(3))(3)] resulted in regioselective insertion of the [Pt(PEt(3))(2)] fragment into the Sn-C(ipso) bond between the tin atom and the seven-membered ring, which afforded the platinastanna[2]troticenophane 5. Oxidative addition was also observed upon treatment of 4 with elemental sulfur or selenium, to produce the [3]troticenophanes [Ti(η(5)-C(5)H(4)SntBu(2))(η(7)-C(7)H(6)SntBu(2))E] (6: E=S; 7: E=Se). The B-B bond of the bora[2]troticenophane 8 was readily cleaved by reaction with [Pt(PEt(3))(3)] to form the corresponding oxidative addition product [Ti(η(5)-C(5)H(4)BNMe(2))(η(7)-C(7)H(6)BNMe(2))Pt(PEt(3))(2)] (9). The solid-state structures of compounds 5, 6, and 9 were also determined by single-crystal X-ray diffraction.