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5-C4H4S)Cr(CO)3 and (η5-C4H4Se)Cr(CO)3: A DFT investigation of the ground-state singlet and triplet surfaces. New insights into the mechanism of C-S or C-Se insertion reactions

Lookup NU author(s): Dr Mohammed Alamiry


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The singlet and triplet surfaces for the interaction of thiophene or selenophene with a chromium tricarbonyl unit were calculated using the B3LYP/LanL2DZ+p model chemistry. The singlet surfaces confirm that the (η5-C4H4E)Cr(CO)3 (E = S or Se) are the lowest energy species. The (η1(C2)-C4H 4E)Cr(CO)3 and (K2(E,C)-C4H 4E)Cr(CO)3 species were also located in shallow energy minima. Reaction path modeling on the singlet surfaces provided activation energies for the endothermic insertion process of 172 and 160 kJ mol -1 for E = S or Se, respectively. The activation energy for the insertion process on the triplet surfaces is on the order of 70 kJ mol -1. A novel η3(E,C,C)-η1(C)-coordinated species was located as a transition state between the insertion species and (η5-C4H4E)Cr(CO)3 on the singlet surfaces and an intermediate on the triplet surface for E = S. © 2009 American Chemical Society.

Publication metadata

Author(s): Alamiry MAH, Brennan P, Coleman A, Long C, Pryce MT

Publication type: Article

Publication status: Published

Journal: Organometallics

Year: 2009

Volume: 28

Issue: 1

Pages: 94-99

ISSN (print): 0276-7333

ISSN (electronic): 1520-6041

Publisher: American Chemical Society


DOI: 10.1021/om8007794


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