Molecular engineering of solid-state materials: Organometallic building blocks

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

Research output: Contribution to journalArticle

Abstract

The syntheses of the reagents [Cp*Ru(CH3CN)3]+(OTf-) (1) (Cp* = η-C5(CH3)5; OTf = CF3SO3) and [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-[2 2]-1,4-cyclophane)]2+(OTf-)2, [Cp*Ru([22]-1,4-cyclophane)CoCp*]3+(OTf -)3, and {[Cp*Ru(η66-[2 2]-1,4-cyclophane)]2Ru}4+(OTf-) 4 have been synthesized. With triptycene as a template, a triangular trication isolated as the complex [(Cp*Ru)366η 6-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. A 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)6666666-p-sexiphenyl)]6+(OTf-)6, respectively. A single-crystal X-ray analysis of the complex [(Cp*Ru)46666-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
StatePublished - 1989

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X ray analysis
Organometallics
X-Rays
Single crystals
Silanes
Aromatic Hydrocarbons
Ruthenium
Aromatic hydrocarbons
Benzene
Atoms
Geometry
p-sexiphenyl
triptycene
cyclophane 1

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Molecular engineering of solid-state materials : Organometallic building blocks. / Fagan, Paul J.; Ward, Michael; Calabrese, Joseph C.

In: Journal of the American Chemical Society, Vol. 111, No. 5, 1989, p. 1698-1719.

Research output: Contribution to journalArticle

@article{6ba552af5c1a4bcbac617df6f6e36508,
title = "Molecular engineering of solid-state materials: Organometallic building blocks",
abstract = "The syntheses of the reagents [Cp*Ru(CH3CN)3]+(OTf-) (1) (Cp* = η-C5(CH3)5; OTf = CF3SO3) and [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)2(η6,η6-[2 2]-1,4-cyclophane)]2+(OTf-)2, [Cp*Ru([22]-1,4-cyclophane)CoCp*]3+(OTf -)3, and {[Cp*Ru(η6,η6-[2 2]-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,η6η 6-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) {\AA}, b = 12.826 (2) {\AA}, c = 24.944 (3) {\AA}, β = 93.49 (1)°, V = 7227.6 {\AA}3, 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. A 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) {\AA}, b = 16.539 (4) {\AA}, c = 17.817 (3) {\AA}, α = 65.47 (2)°, β = 61.82 (2)°, γ = 63.86 (3)°, V = 3552.2 {\AA}3, 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,η 6,η6-p-quaterphenyl)]4+(OTf -)4 and hexacation [(Cp*Ru)6(η6,η6,η 6,η6,η6,η 6-p-sexiphenyl)]6+(OTf-)6, respectively. A single-crystal X-ray analysis of the complex [(Cp*Ru)4(η6,η6,η 6,η6-p-quaterphenyl)](OTf)4 has been performed (triclinic, P1 (No. 2); a = 12.897 (3) {\AA}, b = 13.630 (2) {\AA}, c = 11.906 (2) {\AA}, α = 108.31 (1)°, β = 107.39 (2)°, γ = 100.38 (1)°, V = 1807.3 {\AA}3, Z = 1). The potential use of these complexes for the rational control and preparation of solid-state molecular materials is discussed.",
author = "Fagan, {Paul J.} and Michael Ward and Calabrese, {Joseph C.}",
year = "1989",
language = "English (US)",
volume = "111",
pages = "1698--1719",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "5",

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TY - JOUR

T1 - Molecular engineering of solid-state materials

T2 - Organometallic building blocks

AU - Fagan, Paul J.

AU - Ward, Michael

AU - Calabrese, Joseph C.

PY - 1989

Y1 - 1989

N2 - The syntheses of the reagents [Cp*Ru(CH3CN)3]+(OTf-) (1) (Cp* = η-C5(CH3)5; OTf = CF3SO3) and [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)2(η6,η6-[2 2]-1,4-cyclophane)]2+(OTf-)2, [Cp*Ru([22]-1,4-cyclophane)CoCp*]3+(OTf -)3, and {[Cp*Ru(η6,η6-[2 2]-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,η6η 6-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. A 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)4(η6,η6,η 6,η6-p-quaterphenyl)]4+(OTf -)4 and hexacation [(Cp*Ru)6(η6,η6,η 6,η6,η6,η 6-p-sexiphenyl)]6+(OTf-)6, respectively. A single-crystal X-ray analysis of the complex [(Cp*Ru)4(η6,η6,η 6,η6-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.

AB - The syntheses of the reagents [Cp*Ru(CH3CN)3]+(OTf-) (1) (Cp* = η-C5(CH3)5; OTf = CF3SO3) and [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)2(η6,η6-[2 2]-1,4-cyclophane)]2+(OTf-)2, [Cp*Ru([22]-1,4-cyclophane)CoCp*]3+(OTf -)3, and {[Cp*Ru(η6,η6-[2 2]-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,η6η 6-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. A 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)4(η6,η6,η 6,η6-p-quaterphenyl)]4+(OTf -)4 and hexacation [(Cp*Ru)6(η6,η6,η 6,η6,η6,η 6-p-sexiphenyl)]6+(OTf-)6, respectively. A single-crystal X-ray analysis of the complex [(Cp*Ru)4(η6,η6,η 6,η6-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.

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