Molecular Engineering of Solid-State Materials: Organometallic Building Blocks

Paul J. Fagan, Michael D. Ward, Joseph C. Calabrese

Research output: Contribution to journalArticle

Abstract

The syntheses of the reagents [Cp*Ru(CH3CN3)]+(OTf-) (1) (Cp* = η-C5(CH3)5; OTf = CF3SO3and [Cp*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)266-[22]-1,4-cyclophane)]2+(OTf-)2, [Cp*Ru([22]-1,4-cyclophane)CoCp*]3+(OTf-)3, and ([Cp*Ru(η66-[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)3666-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 {[Cp*Ru(η-C6H5)]4E}4+(OTf-)4 (E = C, Si, Ge, Sn, Pb). The structure of {[Cp*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) Å, b = 12.826 (2) Å, c = 24.944 (3) Å, β = 93.49 (1)°, V = 7227.6 Å3, Z = 4) and is compared to the structural parameters of the tetracations {[Cp*Ru(η-C6H5)]4E}4+ (E = C, Si). Reaction of 1 with hexakis(p-methoxyphenoxy)benzene yields |[Cp*Ru(p-CH3O-η-C6H4-O)]6C6)6+(OTf-)6. Å single-crystal X-ray analysis of {[Cp*Ru(p-CH3O-η-C6H4-O)]6C6)(OTf)6•6CH3NO2 (triclinic, P1 (No. 2); a = 15.784 (3) Å, b = 16.539 (4) Å, c = 17.817 (3) Å, α = 65.47 (2)°, β = 61.82 (2)°, γ = 63.86 (3)°, V= 3552.2 Å3, 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)46666-p-quaterphenyl)]4+(OTf-)4 and hexacation [(Cp*Ru)6-(η66666-p-sexiphenyl)]6+(OTf-)6, respectively. A single-crystal X-ray analysis of the complex [(Cp*Ru)4-(η6666-p-quaterphenyl)](OTf-)4 has been performed (triclinic, P1 (No. 2); a = 12.897 (3) Å, b = 13.630 (2) Å, c - 11.906 (2) Å, α = 108.31 (1)°, β = 107.39 (2)°, γ= 100.38 (1)°, V= 1807.3 Å3, Z = 1). The potential use of these complexes for the rational control and preparation of solid-state molecular materials is discussed.

Original languageEnglish (US)
Pages (from-to)1698-1719
Number of pages22
JournalJournal of the American Chemical Society
Volume111
Issue number5
DOIs
StatePublished - Mar 1989

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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