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Dcab(2-) - Substituted manganese vinylidene complexes as better electron reservoirs: A DFT study

Satpati, Priyadarshi (2007) Dcab(2-) - Substituted manganese vinylidene complexes as better electron reservoirs: A DFT study. In: Organometallics, 26 (19). pp. 4771-4775.

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Official URL: http://pubs.acs.org/doi/pdf/10.1021/om700327b

Abstract

Mononuclear vinylidene complexes of the type Mn(C5H4R')(R"2PCH2CH2P R"(2))= C = C(R')(H) are synthesized and reported by Venkatesan et a]. as potential electron reservoirs, which can store and release electrons in a reversible fashion. However, the slow oxidation of the parent compound leads to an undesired product. In our model compound Mn(C5H5)(PH3)(2 =)C = C(R)(H), we substituted the cyclopentadienyl moiety by the isolobal dianionic dicarbollyl ligand Dcab(2-) (C2B9H112-) and investigated whether this simple substitution can reduce the production of an undesired product. Our calculations of vertical electron detachment energy, thermodynamic feasibility, and molecular orbital analysis (with substituents R = H, Me, Ph on the Cp atom of our model system) show that the substitution is thermodynamically favorable and leads to easy oxidation of the parent compound, easy dimerization, and better reversibility. Our comparative study between Mn(C5H5)(PH3)(2 =)C = C(R)(H) and Mn(Dcab)(PH3)(2) = C = C(R)(H)(-) (where R = H. Me, Ph) predicts the latter to be a better electronic reservoir.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to American Chemical Society.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 12 Mar 2009 11:52
Last Modified: 19 Sep 2010 05:01
URI: http://eprints.iisc.ernet.in/id/eprint/18401

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