Molecular Engineering of Solid-State Materials: Organometallic Building Blocks

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

doi:10.1021/ja00187a024

Molecular Engineering of Solid-State Materials: Organometallic Building Blocks

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

Chemistry

Research output: Contribution to journal › Article › peer-review

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)₂(η⁶,η⁶-[2₂]-1,4-cyclophane)]²⁺(OTf^-)2, [Cp*Ru([2₂]-1,4-cyclophane)CoCp*]³⁺(OTf^-)₃, and ([Cp*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 {[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)₄(η⁶,η⁶,η⁶,η⁶-p-quaterphenyl)]⁴⁺(OTf^-)₄ and hexacation [(Cp*Ru)₆-(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, 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 language	English (US)
Pages (from-to)	1698-1719
Number of pages	22
Journal	Journal of the American Chemical Society
Volume	111
Issue number	5
DOIs	https://doi.org/10.1021/ja00187a024
State	Published - Mar 1989

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/ja00187a024

Cite this

@article{6ba552af5c1a4bcbac617df6f6e36508,

title = "Molecular Engineering of Solid-State Materials: Organometallic Building Blocks",

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)2(η6,η6-[22]-1,4-cyclophane)]2+(OTf-)2, [Cp*Ru([22]-1,4-cyclophane)CoCp*]3+(OTf-)3, and ([Cp*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 {[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. {\AA} 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,η6,η6-p-quaterphenyl)]4+(OTf-)4 and hexacation [(Cp*Ru)6-(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, 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 Ward, {Michael D.} and Calabrese, {Joseph C.}",

year = "1989",

month = mar,

doi = "10.1021/ja00187a024",

language = "English (US)",

volume = "111",

pages = "1698--1719",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "5",

}

TY - JOUR

T1 - Molecular Engineering of Solid-State Materials

T2 - Organometallic Building Blocks

AU - Fagan, Paul J.

AU - Ward, Michael D.

AU - Calabrese, Joseph C.

PY - 1989/3

Y1 - 1989/3

N2 - 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)2(η6,η6-[22]-1,4-cyclophane)]2+(OTf-)2, [Cp*Ru([22]-1,4-cyclophane)CoCp*]3+(OTf-)3, and ([Cp*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 {[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)4(η6,η6,η6,η6-p-quaterphenyl)]4+(OTf-)4 and hexacation [(Cp*Ru)6-(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, 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(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)2(η6,η6-[22]-1,4-cyclophane)]2+(OTf-)2, [Cp*Ru([22]-1,4-cyclophane)CoCp*]3+(OTf-)3, and ([Cp*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 {[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)4(η6,η6,η6,η6-p-quaterphenyl)]4+(OTf-)4 and hexacation [(Cp*Ru)6-(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, 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.

UR - http://www.scopus.com/inward/record.url?scp=0024622017&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0024622017&partnerID=8YFLogxK

U2 - 10.1021/ja00187a024

DO - 10.1021/ja00187a024

M3 - Article

AN - SCOPUS:0024622017

SN - 0002-7863

VL - 111

SP - 1698

EP - 1719

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 5

ER -

Molecular Engineering of Solid-State Materials: Organometallic Building Blocks

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this