Molecular Engineering of Solid-State Materials: Organometallic Building Blocks

Article abstract of DOI:10.1021/ja00187a024

The syntheses of the reagents *Ru(CH3CN)3>(+)(OTf(-)) (1) (Cp^* = η-C5(CH3)5; OTf = CF3SO3) and *Ru(μ₃-Cl)>4 (2) are reported.Reaction of 1 with aromatic hydrocarbons that are used as geometric templates allows the preparation of polycationic complexes with particular shapes and geometries of positive charge.Using <2₂>-1,4-cyclophane, the cylindrical rod-like complexes <(Cp^*Ru)2(η⁶,η⁶-<2₂>-1,4-cyclophane)>(2+)(OTf(-))2, *Ru(<2₂>-1,4-cyclophane)CoCp^*>(3+)(OTf(-))3, and <*Ru(η⁶,η⁶-<2₂>-1,4-cyclophane)>2Ru>(4+)(OTf(-))4 have been synthesized.With triptycene as a template, a triangular trication isolated as the complex <(Cp^*Ru)3(η⁶,η⁶,η⁶-triptycene)>(3+)(OTf(-))3 can be prepared.Reaction of 1 with tetraphenylmethane, -silane, -germane, -stannane, and -plumbane results in formation of tetrahedral tetracations isolated as the complexes <*Ru(η-C6H5)>4E>(4+)(OTf(-))4 (E = C, Si, Ge, Sn, Pb).The structure of <*Ru(η-C6H5)>4Ge>(4+)(OTf(-))4 has been determined by a single-crystal X-ray analysis (monoclinic-b, P2₁/c (No. 14); a = 22.633 (3) Angstroem, b = 12.826 (2) Angstroem, c = 24.944 (3) Angstroem, β = 93.49 (1)deg, V = 7227.6 Angstroem³, Z = 4) and is compared to the structural parameters of the tetracations <*Ru(η-C6H5)>4E>(4+) (E = C, Si).Reaction of 1 with hexakis(p-methoxyphenoxy)benzene yields <*Ru(p-CH3O-η-C6H4-O)>6C6>(6+)(OTf(-))6.A single-crystal X-ray analysis of <*Ru(p-CH3O-η-C6H4-O)>6C6>(OTf)6*6CH3NO2 (triclinic, P<*> (No. 2); a = 15.784 (3) Angstroem, b = 16.539 (4) Angstroem, c = 17.817 (3) Angstroem, α = 65.47 (2)deg, β = 61.82 (2)deg, γ = 63.86 (3)deg, V = 3552.2 Angstroem³, Z = 1) shows that the hexacation contains an octahedral array of ruthenium atoms.With p-quaterphenyl and p-sexiphenyl, the reaction with 1 leads to formation of the tetracation <(Cp^*Ru)4(η⁶,η⁶,η⁶,η⁶-p-quaterphenyl)>(4+)(OTf(-))4 and hexacation <(Cp^*Ru)6(η⁶,η⁶,η⁶,η⁶,η⁶,η⁶-p-sexiphenyl)>(6+)(OTf(-))6, respectively.A single-crystal X-ray analysis of the complex <(Cp^*Ru)4(η⁶,η⁶,η⁶,η⁶-p-quaterphenyl)>(OTf)4 has been performed (triclinic, P<*> (No. 2); a = 12.897 (3) Angstroem, b = 13.630 (2) Angstroem, c = 11.906 (2) Angstroem, α = 108.31 (1)deg, β = 107.39 (2)deg, γ = 100.38 (1)deg, V = 1807.3 Angstroem³, Z = 1).The potential use of these complexes for the rational control and preparation of solid-state molecular materials is discussed.