Electronic structure of the 2.4-diphosphacyclobutane-diyl-1.3 and substituted derivatives

Schoeller W, Begemann C, Niecke E, Gudat D (2001)
JOURNAL OF PHYSICAL CHEMISTRY A 105(47): 10731-10738.

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Zeitschriftenaufsatz | Veröffentlicht | Englisch
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Abstract / Bemerkung
The electronic structure of the 2.4-diphosphacyclobutanediyl-1.3 and its substituted compounds were investigated by various electron-correlated quantum chemical ab initio calculations, at the MCSCF, MP2, and MR-MP2 levels, and compared with the results of RHF level calculations. The structure is in essence a biradical (biradicaloid) species with partial pi -delocalization within the ring system. A problem occurs with the description of this species by the MCSCF approach. A limited active configuration space overestimates the biradical nature of the structure. A satisfactory description is given by the MP2 procedure which also takes proper account for the dynamical part of the correlation energy correction to the resulting wave function. A bicyclic structure is more stable than a ring structure. A phosphino-carbene analogous structure is only slightly less stable than the ring structure. A detailed study of the substituent effects indicates that silyl groups at carbon tend to increase considerably the stability of a singlet ground state over a triplet ground state. Bonding within the ring system is discussed in terms of biradical or cyclic delocalized canonical structures.
Erscheinungsjahr
Zeitschriftentitel
JOURNAL OF PHYSICAL CHEMISTRY A
Band
105
Zeitschriftennummer
47
Seite
10731-10738
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eISSN
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Schoeller W, Begemann C, Niecke E, Gudat D. Electronic structure of the 2.4-diphosphacyclobutane-diyl-1.3 and substituted derivatives. JOURNAL OF PHYSICAL CHEMISTRY A. 2001;105(47):10731-10738.
Schoeller, W., Begemann, C., Niecke, E., & Gudat, D. (2001). Electronic structure of the 2.4-diphosphacyclobutane-diyl-1.3 and substituted derivatives. JOURNAL OF PHYSICAL CHEMISTRY A, 105(47), 10731-10738. doi:10.1021/jp0117009
Schoeller, W., Begemann, C., Niecke, E., and Gudat, D. (2001). Electronic structure of the 2.4-diphosphacyclobutane-diyl-1.3 and substituted derivatives. JOURNAL OF PHYSICAL CHEMISTRY A 105, 10731-10738.
Schoeller, W., et al., 2001. Electronic structure of the 2.4-diphosphacyclobutane-diyl-1.3 and substituted derivatives. JOURNAL OF PHYSICAL CHEMISTRY A, 105(47), p 10731-10738.
W. Schoeller, et al., “Electronic structure of the 2.4-diphosphacyclobutane-diyl-1.3 and substituted derivatives”, JOURNAL OF PHYSICAL CHEMISTRY A, vol. 105, 2001, pp. 10731-10738.
Schoeller, W., Begemann, C., Niecke, E., Gudat, D.: Electronic structure of the 2.4-diphosphacyclobutane-diyl-1.3 and substituted derivatives. JOURNAL OF PHYSICAL CHEMISTRY A. 105, 10731-10738 (2001).
Schoeller, Wolfgang, Begemann, C, Niecke, E, and Gudat, D. “Electronic structure of the 2.4-diphosphacyclobutane-diyl-1.3 and substituted derivatives”. JOURNAL OF PHYSICAL CHEMISTRY A 105.47 (2001): 10731-10738.