Heavy ferrocene: A sandwich complex containing Si and Ge atoms

Vladimir Ya Lee; Risa Kato; Akira Sekiguchi; Andreas Krapp; Gernot Frenking

doi:10.1021/ja0740162

Heavy ferrocene: A sandwich complex containing Si and Ge atoms

Vladimir Ya Lee, Risa Kato, Akira Sekiguchi, Andreas Krapp, Gernot Frenking

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48 Scopus citations

Abstract

The heavy analogue of ferrocene (η⁵-Me₅C₅)Fe[η⁵-(CPh)(CH)Si₂Ge(SiMe^tBu₂)₃] 2, incorporating three heavy group 14 elements in one of the cyclopentadienyl rings, was synthesized by the reaction of the heavy lithium cyclopentadienide [η⁵-(CPh)(CH)Si₂Ge(SiMetBu₂)₃]·[Li⁺(thf)] 1-·[Li+(thf)] with (η⁵-Me₅C₅)Fe(acac) in THF. The crystal structure analysis of 2 revealed a remarkable flattening of the C₂Si₂Ge five-membered ring, taking place upon complexation, in which the lengths of all skeletal bonds were intermediate between those of the typical single and double bonds. The one-electron oxidation of 2 occurred at more negative potentials than that of the parent (η⁵-Me5C5)2Fe: -0.53 versus -0.32 V. The fragment MO and energy decomposition analyses revealed that the bonding in 2 is predominantly electrostatic, whereas the most important covalent bonding contribution comes from the heavy Cp^- ligand to CpFe⁺ fragment π-donation.

Original language	English
Pages (from-to)	10340-10341
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	129
Issue number	34
DOIs	https://doi.org/10.1021/ja0740162
State	Published - 29 Aug 2007
Externally published	Yes

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title = "Heavy ferrocene: A sandwich complex containing Si and Ge atoms",

abstract = "The heavy analogue of ferrocene (η5-Me5C5)Fe[η5-(CPh)(CH)Si2Ge(SiMetBu2)3] 2, incorporating three heavy group 14 elements in one of the cyclopentadienyl rings, was synthesized by the reaction of the heavy lithium cyclopentadienide [η5-(CPh)(CH)Si2Ge(SiMetBu2)3]·[Li+(thf)] 1-·[Li+(thf)] with (η5-Me5C5)Fe(acac) in THF. The crystal structure analysis of 2 revealed a remarkable flattening of the C2Si2Ge five-membered ring, taking place upon complexation, in which the lengths of all skeletal bonds were intermediate between those of the typical single and double bonds. The one-electron oxidation of 2 occurred at more negative potentials than that of the parent (η5-Me5C5)2Fe: -0.53 versus -0.32 V. The fragment MO and energy decomposition analyses revealed that the bonding in 2 is predominantly electrostatic, whereas the most important covalent bonding contribution comes from the heavy Cp- ligand to CpFe+ fragment π-donation.",

author = "Lee, {Vladimir Ya} and Risa Kato and Akira Sekiguchi and Andreas Krapp and Gernot Frenking",

year = "2007",

month = aug,

day = "29",

doi = "10.1021/ja0740162",

language = "英语",

volume = "129",

pages = "10340--10341",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Heavy ferrocene

T2 - A sandwich complex containing Si and Ge atoms

AU - Lee, Vladimir Ya

AU - Kato, Risa

AU - Sekiguchi, Akira

AU - Krapp, Andreas

AU - Frenking, Gernot

PY - 2007/8/29

Y1 - 2007/8/29

N2 - The heavy analogue of ferrocene (η5-Me5C5)Fe[η5-(CPh)(CH)Si2Ge(SiMetBu2)3] 2, incorporating three heavy group 14 elements in one of the cyclopentadienyl rings, was synthesized by the reaction of the heavy lithium cyclopentadienide [η5-(CPh)(CH)Si2Ge(SiMetBu2)3]·[Li+(thf)] 1-·[Li+(thf)] with (η5-Me5C5)Fe(acac) in THF. The crystal structure analysis of 2 revealed a remarkable flattening of the C2Si2Ge five-membered ring, taking place upon complexation, in which the lengths of all skeletal bonds were intermediate between those of the typical single and double bonds. The one-electron oxidation of 2 occurred at more negative potentials than that of the parent (η5-Me5C5)2Fe: -0.53 versus -0.32 V. The fragment MO and energy decomposition analyses revealed that the bonding in 2 is predominantly electrostatic, whereas the most important covalent bonding contribution comes from the heavy Cp- ligand to CpFe+ fragment π-donation.

AB - The heavy analogue of ferrocene (η5-Me5C5)Fe[η5-(CPh)(CH)Si2Ge(SiMetBu2)3] 2, incorporating three heavy group 14 elements in one of the cyclopentadienyl rings, was synthesized by the reaction of the heavy lithium cyclopentadienide [η5-(CPh)(CH)Si2Ge(SiMetBu2)3]·[Li+(thf)] 1-·[Li+(thf)] with (η5-Me5C5)Fe(acac) in THF. The crystal structure analysis of 2 revealed a remarkable flattening of the C2Si2Ge five-membered ring, taking place upon complexation, in which the lengths of all skeletal bonds were intermediate between those of the typical single and double bonds. The one-electron oxidation of 2 occurred at more negative potentials than that of the parent (η5-Me5C5)2Fe: -0.53 versus -0.32 V. The fragment MO and energy decomposition analyses revealed that the bonding in 2 is predominantly electrostatic, whereas the most important covalent bonding contribution comes from the heavy Cp- ligand to CpFe+ fragment π-donation.

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U2 - 10.1021/ja0740162

DO - 10.1021/ja0740162

M3 - 文章

AN - SCOPUS:34548233753

SN - 0002-7863

VL - 129

SP - 10340

EP - 10341

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 34

ER -

Heavy ferrocene: A sandwich complex containing Si and Ge atoms

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