Triple-Decker Complexes. 9. Triple-Decker Complexes with Bridging Cyclopentadienyl Ligands and Novel Cyclopentadienyl Transfer Reactions

Gerhard E. Herberich; Ulli Englert; Frank Marken; Peter Hofmann

doi:10.1021/om00034a041

Triple-Decker Complexes. 9. Triple-Decker Complexes with Bridging Cyclopentadienyl Ligands and Novel Cyclopentadienyl Transfer Reactions

Gerhard E. Herberich, Ulli Englert, Frank Marken, Peter Hofmann

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

Abstract

The pentamethylmetallocenes CpMCp* (M = Ru, Fe) react with [Cp*Ru(OMe)]₂/CF₃SO₃H in ether to give triple-decker salts [Cp*M(μ-Cp)RuCp*]CF₃SO₃ (4·CF₃SO₃, M = Ru; 5·CF₃SO₃, M = Fe) with an unsubstituted Cp as the bridging ligand. The structure of 4·CF₃SO₃-THF shows average metal-ring distances of 177.6(1) pm for the outer Cp* ligands and of 185.5(1) pm for the bridging Cp ring. The metalloelectrophiles [LM(solv)₃]²⁺, generated from the dichlorides [(C₆Me₆)RuCl₂]₂, (Cp*RhCl₂)₂, (Cp*IrCl₂)₂, [(C₄Me₄)PtCl₂]₂, and AgCF₃SO₃ in MeNO₂-d₃, react with CpRuCp* at room temperature to undergo novel cyclopentadienyl transfer reactions, thus forming the cations [LMCp]⁺ besides 4⁺. With CpFeCp* labile triple-decker dications [LMCpFeCp*]²⁺” are formed in MeNO₂-d₃ at 0 °C while at higher temperature cyclopentadienyl transfer (for Ru, Ir) or alternatively redox reactions (for Rh, Pt) are observed. [(C₆Me₅)Ru(acetone)₃] (CF₃SO₃)₂ reacts with Fe(C₅H₄CHO)₂ in acetone to give, after crystallization from CHC1₃, [(C₆Me₆)Ru(C₆H₄CHO)]CF₃SO₃-CHCl₃ (70%). Extended Hückel MO calculations for CpFeCp* reveal weaker bonds to the Cp side and an asymmetric charge distribution with total net charges of −0.093 for the Cp and +0.104 for the Cp* fragments. This suggests that the observed regiochemistry of the stacking and ring ligand transfer reactions of 1 and 2 is primarily of electronic origin.

Original language	English
Pages (from-to)	4039-4045
Number of pages	7
Journal	Organometallics
Volume	12
Issue number	10
DOIs	https://doi.org/10.1021/om00034a041
Publication status	Published - 1 Oct 1993

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{e3d2629783f14897a34abbaa6598a0fd,

title = "Triple-Decker Complexes. 9. Triple-Decker Complexes with Bridging Cyclopentadienyl Ligands and Novel Cyclopentadienyl Transfer Reactions",

abstract = "The pentamethylmetallocenes CpMCp* (M = Ru, Fe) react with [Cp*Ru(OMe)]2/CF3SO3H in ether to give triple-decker salts [Cp*M(μ-Cp)RuCp*]CF3SO3 (4·CF3SO3, M = Ru; 5·CF3SO3, M = Fe) with an unsubstituted Cp as the bridging ligand. The structure of 4·CF3SO3-THF shows average metal-ring distances of 177.6(1) pm for the outer Cp* ligands and of 185.5(1) pm for the bridging Cp ring. The metalloelectrophiles [LM(solv)3]2+, generated from the dichlorides [(C6Me6)RuCl2]2, (Cp*RhCl2)2, (Cp*IrCl2)2, [(C4Me4)PtCl2]2, and AgCF3SO3 in MeNO2-d3, react with CpRuCp* at room temperature to undergo novel cyclopentadienyl transfer reactions, thus forming the cations [LMCp]+ besides 4+. With CpFeCp* labile triple-decker dications [LMCpFeCp*]2+” are formed in MeNO2-d3 at 0 °C while at higher temperature cyclopentadienyl transfer (for Ru, Ir) or alternatively redox reactions (for Rh, Pt) are observed. [(C6Me5)Ru(acetone)3] (CF3SO3)2 reacts with Fe(C5H4CHO)2 in acetone to give, after crystallization from CHC13, [(C6Me6)Ru(C6H4CHO)]CF3SO3-CHCl3 (70%). Extended H{\"u}ckel MO calculations for CpFeCp* reveal weaker bonds to the Cp side and an asymmetric charge distribution with total net charges of −0.093 for the Cp and +0.104 for the Cp* fragments. This suggests that the observed regiochemistry of the stacking and ring ligand transfer reactions of 1 and 2 is primarily of electronic origin.",

author = "Herberich, {Gerhard E.} and Ulli Englert and Frank Marken and Peter Hofmann",

year = "1993",

month = oct,

day = "1",

doi = "10.1021/om00034a041",

language = "English",

volume = "12",

pages = "4039--4045",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "10",

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TY - JOUR

T1 - Triple-Decker Complexes. 9. Triple-Decker Complexes with Bridging Cyclopentadienyl Ligands and Novel Cyclopentadienyl Transfer Reactions

AU - Herberich, Gerhard E.

AU - Englert, Ulli

AU - Marken, Frank

AU - Hofmann, Peter

PY - 1993/10/1

Y1 - 1993/10/1

N2 - The pentamethylmetallocenes CpMCp* (M = Ru, Fe) react with [Cp*Ru(OMe)]2/CF3SO3H in ether to give triple-decker salts [Cp*M(μ-Cp)RuCp*]CF3SO3 (4·CF3SO3, M = Ru; 5·CF3SO3, M = Fe) with an unsubstituted Cp as the bridging ligand. The structure of 4·CF3SO3-THF shows average metal-ring distances of 177.6(1) pm for the outer Cp* ligands and of 185.5(1) pm for the bridging Cp ring. The metalloelectrophiles [LM(solv)3]2+, generated from the dichlorides [(C6Me6)RuCl2]2, (Cp*RhCl2)2, (Cp*IrCl2)2, [(C4Me4)PtCl2]2, and AgCF3SO3 in MeNO2-d3, react with CpRuCp* at room temperature to undergo novel cyclopentadienyl transfer reactions, thus forming the cations [LMCp]+ besides 4+. With CpFeCp* labile triple-decker dications [LMCpFeCp*]2+” are formed in MeNO2-d3 at 0 °C while at higher temperature cyclopentadienyl transfer (for Ru, Ir) or alternatively redox reactions (for Rh, Pt) are observed. [(C6Me5)Ru(acetone)3] (CF3SO3)2 reacts with Fe(C5H4CHO)2 in acetone to give, after crystallization from CHC13, [(C6Me6)Ru(C6H4CHO)]CF3SO3-CHCl3 (70%). Extended Hückel MO calculations for CpFeCp* reveal weaker bonds to the Cp side and an asymmetric charge distribution with total net charges of −0.093 for the Cp and +0.104 for the Cp* fragments. This suggests that the observed regiochemistry of the stacking and ring ligand transfer reactions of 1 and 2 is primarily of electronic origin.

AB - The pentamethylmetallocenes CpMCp* (M = Ru, Fe) react with [Cp*Ru(OMe)]2/CF3SO3H in ether to give triple-decker salts [Cp*M(μ-Cp)RuCp*]CF3SO3 (4·CF3SO3, M = Ru; 5·CF3SO3, M = Fe) with an unsubstituted Cp as the bridging ligand. The structure of 4·CF3SO3-THF shows average metal-ring distances of 177.6(1) pm for the outer Cp* ligands and of 185.5(1) pm for the bridging Cp ring. The metalloelectrophiles [LM(solv)3]2+, generated from the dichlorides [(C6Me6)RuCl2]2, (Cp*RhCl2)2, (Cp*IrCl2)2, [(C4Me4)PtCl2]2, and AgCF3SO3 in MeNO2-d3, react with CpRuCp* at room temperature to undergo novel cyclopentadienyl transfer reactions, thus forming the cations [LMCp]+ besides 4+. With CpFeCp* labile triple-decker dications [LMCpFeCp*]2+” are formed in MeNO2-d3 at 0 °C while at higher temperature cyclopentadienyl transfer (for Ru, Ir) or alternatively redox reactions (for Rh, Pt) are observed. [(C6Me5)Ru(acetone)3] (CF3SO3)2 reacts with Fe(C5H4CHO)2 in acetone to give, after crystallization from CHC13, [(C6Me6)Ru(C6H4CHO)]CF3SO3-CHCl3 (70%). Extended Hückel MO calculations for CpFeCp* reveal weaker bonds to the Cp side and an asymmetric charge distribution with total net charges of −0.093 for the Cp and +0.104 for the Cp* fragments. This suggests that the observed regiochemistry of the stacking and ring ligand transfer reactions of 1 and 2 is primarily of electronic origin.

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DO - 10.1021/om00034a041

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Triple-Decker Complexes. 9. Triple-Decker Complexes with Bridging Cyclopentadienyl Ligands and Novel Cyclopentadienyl Transfer Reactions

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