Theoretical Prediction on [5]Radialene Sandwich Complexes (CpM) 2 (C 10 H 10 ) (Cp = η 5 -C 5 H 5 ; M = Fe, Co, Ni): Geometry, Spin States, and Bonding
[5]Radialene, the missing link for synthesis of radialene family, has been finally obtained via the preparation and decomplexation of the [5]radialene-bis-Fe(CO) complex. The stability of [5]radialene complex benefits from the coordination with Fe(CO) by losing free 1,3-butadiene structures to avoid...
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| Veröffentlicht in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Jg. 121; H. 5; S. 1106 |
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| Hauptverfasser: | , , |
| Format: | Journal Article |
| Sprache: | Englisch |
| Veröffentlicht: |
United States
09.02.2017
|
| ISSN: | 1520-5215 |
| Online-Zugang: | Weitere Angaben |
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| Zusammenfassung: | [5]Radialene, the missing link for synthesis of radialene family, has been finally obtained via the preparation and decomplexation of the [5]radialene-bis-Fe(CO)
complex. The stability of [5]radialene complex benefits from the coordination with Fe(CO)
by losing free 1,3-butadiene structures to avoid polymerization. In light of the similar coordination ability of half-sandwiches CpM(Cp = η
-C
H
; M = Fe, Co, Ni), there is a great possibility that the sandwiched complexes of [5]radialene with CpM are available. Herein, we present the first theoretical prediction on the geometry, spin states and bonding of (CpM)(C
H
) and (CpM)
(C
H
). For M = Fe, Co, Ni, the ground states of (CpM)(C
H
) and (CpM)
(C
H
) are doublet and triplet, singlet and singlet, and doublet and triplet states, where each Fe, Co, and Ni adopts 17, 18, and 19 electron-configuration, respectively. In particular, (CpFe)
(C
H
) and (CpNi)
(C
H
) have considerable open-shell singlet features. Generally the trans isomers of (CpM)
(C
H
) with two CpM fragments on the opposite sides of the [5]radialene plane are apparently more stable than the cis ones with CpM fragments on the same side. However, for the singlet and triplet isomers of (CpNi)
(C
H
) (both cis and trans isomers), the energy differences are relatively small, indicating that these isomers all have the opportunity to exist. Besides, the easy Diels-Alder (DA) dimerization between the [3]dendralene-like fragments of (CpM)(C
H
) suggests the great difficulty in isolating the (CpM)(C
H
) monomer. |
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| ISSN: | 1520-5215 |
| DOI: | 10.1021/acs.jpca.6b11066 |