P nRing Size Dependence on NHC-Induced Ring Contraction Reactions of [CoCp'(η4-P4)], [Ta(CO)2Cp″( η4-P4)], and [FeCp*(η5-P5)]: A DFT Study

Joshi, G and Sreerag, MN and Jemmis, ED and Nixon, JF (2022) P nRing Size Dependence on NHC-Induced Ring Contraction Reactions of [CoCp'(η4-P4)], [Ta(CO)2Cp″( η4-P4)], and [FeCp*(η5-P5)]: A DFT Study. In: Inorganic Chemistry, 61 (40). 15822- 15830.

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Abstract

The facile ring contraction of [CoCp' (η4-P4)] and [Ta(CO)2Cp″( η4-P4)] to [CoCp' (η3-P3)][(MeNHC)2P] and [Ta(CO)2Cp″( η3-P3)] [(MeNHC)2P] induced by MeNHC and the absence of the ring contraction of [FeCp*(η5-P5)] under the same conditions are studied by density functional theory (DFT) computations. The latter is estimated to be thermodynamically the least favorable reaction and also has a very high energy barrier. The similar strain energies of P3and P4rings and the lower strain energy of the P5ring play a decisive role in the ring contraction capability of these [TM-cyclo-Pn] complexes. Theoretical approaches involving NBO and IBO analysis have been employed to provide a qualitative picture of the overall reactions. The role of substituents and the nature of transition metals in determining the energetics of these reactions has also been studied and an isolobal perspective on these systems affords a simplified picture.

Item Type:	Journal Article
Publication:	Inorganic Chemistry
Publisher:	American Chemical Society
Additional Information:	The copyright for this article belongs to American Chemical Society.
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	31 Oct 2022 11:18
Last Modified:	31 Oct 2022 11:18
URI:	https://eprints.iisc.ac.in/id/eprint/77682

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