Theoretical Study of the Nature of the (Eta 5-Cyclopentadienyl) dicarbonyliron–Arene Bond. Significance of the π Interaction

Nancy A. Richardson; Michael B Hall

Theoretical Study of the Nature of the (Eta 5-Cyclopentadienyl) dicarbonyliron–Arene Bond. Significance of the π Interaction

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Abstract

<div class="line" id="line-7"> The substituent–arene orbital interactions in 1,4-C6H4Fp2 where Fp = (&boxDl;5-C5H5)Fe(CO)2, are compared with the interactions in the series C6H4X2, X=BH2, NH2, CH2 and O, by using unparameterized Fenske-Hall molecular orbital calculations. Analysis of the MOs, the Mulliken populations of the fragments, and the overlap populations provides an understanding of the extent and nature of the relative σ and π interactions between the arene and the various substituents. In our fragment analysis the interactions of the main-group fragments are compared easily with the interactions of the transition-metal fragment. Although it has been suggested that 1,4-C6H4Fp2 has a significant contribution from a quinone-like resonance structure, our study of the bonding reveals very little π character in the Fe–arene bonds.</div>

Original language	American English
Journal	Organometallics
Volume	12
State	Published - Apr 1993

Disciplines

Physical Sciences and Mathematics
Chemistry

Cite this

@article{ef7fe356c7074393bd34e64d1b72fd3b,

title = "Theoretical Study of the Nature of the (Eta 5-Cyclopentadienyl) dicarbonyliron–Arene Bond. Significance of the π Interaction",

abstract = " The substituent–arene orbital interactions in 1,4-C6H4Fp2 where Fp = (&boxDl;5-C5H5)Fe(CO)2, are compared with the interactions in the series C6H4X2, X=BH2, NH2, CH2 and O, by using unparameterized Fenske-Hall molecular orbital calculations. Analysis of the MOs, the Mulliken populations of the fragments, and the overlap populations provides an understanding of the extent and nature of the relative σ and π interactions between the arene and the various substituents. In our fragment analysis the interactions of the main-group fragments are compared easily with the interactions of the transition-metal fragment. Although it has been suggested that 1,4-C6H4Fp2 has a significant contribution from a quinone-like resonance structure, our study of the bonding reveals very little π character in the Fe–arene bonds.",

author = "Richardson, {Nancy A.} and Hall, {Michael B}",

note = "36 (10) , 2018-2022. DOI: 10.1021/ic960813h.",

year = "1993",

month = apr,

language = "American English",

volume = "12",

journal = "Organometallics",

}

TY - JOUR

T1 - Theoretical Study of the Nature of the (Eta 5-Cyclopentadienyl) dicarbonyliron–Arene Bond. Significance of the π Interaction

AU - Richardson, Nancy A.

AU - Hall, Michael B

N1 - 36 (10) , 2018-2022. DOI: 10.1021/ic960813h.

PY - 1993/4

Y1 - 1993/4

N2 - The substituent–arene orbital interactions in 1,4-C6H4Fp2 where Fp = (&boxDl;5-C5H5)Fe(CO)2, are compared with the interactions in the series C6H4X2, X=BH2, NH2, CH2 and O, by using unparameterized Fenske-Hall molecular orbital calculations. Analysis of the MOs, the Mulliken populations of the fragments, and the overlap populations provides an understanding of the extent and nature of the relative σ and π interactions between the arene and the various substituents. In our fragment analysis the interactions of the main-group fragments are compared easily with the interactions of the transition-metal fragment. Although it has been suggested that 1,4-C6H4Fp2 has a significant contribution from a quinone-like resonance structure, our study of the bonding reveals very little π character in the Fe–arene bonds.

AB - The substituent–arene orbital interactions in 1,4-C6H4Fp2 where Fp = (&boxDl;5-C5H5)Fe(CO)2, are compared with the interactions in the series C6H4X2, X=BH2, NH2, CH2 and O, by using unparameterized Fenske-Hall molecular orbital calculations. Analysis of the MOs, the Mulliken populations of the fragments, and the overlap populations provides an understanding of the extent and nature of the relative σ and π interactions between the arene and the various substituents. In our fragment analysis the interactions of the main-group fragments are compared easily with the interactions of the transition-metal fragment. Although it has been suggested that 1,4-C6H4Fp2 has a significant contribution from a quinone-like resonance structure, our study of the bonding reveals very little π character in the Fe–arene bonds.

UR - https://pubs.acs.org/doi/10.1021/om00028a057

M3 - Article

VL - 12

JO - Organometallics

JF - Organometallics

ER -

Theoretical Study of the Nature of the (Eta 5-Cyclopentadienyl) dicarbonyliron–Arene Bond. Significance of the π Interaction

Abstract

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