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Issue 20, 2012
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Manganese carbonyl fluorides: are they viable molecules?

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Abstract

The mononuclear Mn(CO)5X and binuclear Mn2(CO)8(μ-X)2 manganese carbonyl halides have long been known for the halogens Cl, Br, and I. However, the corresponding manganese carbonyl fluorides (X = F) remain unknown. The structures and thermochemistry of such manganese carbonyl fluorides and their decarbonylation products have now been investigated using density functional theory. In all cases singlet structures were found to have lower energies than the corresponding triplet structures. The expected octahedral structure is predicted for Mn(CO)5F. Decarbonylation of Mn(CO)5F is predicted to give trigonal bipyramidal Mn(CO)4F with equatorial fluorine. Further, decarbonylation gives tetrahedral Mn(CO)3F. All of the binuclear Mn2(CO)nF2 structures (n = 8, 7, 6) are predicted to have a central Mn2F2 unit with two bridging F atoms, a non-bonding Mn⋯Mn distance of ∼3.1 Å, and exclusively terminal CO groups. The thermochemistry of these manganese carbonyl fluorides indicates that they are viable species. This suggests that the failure to date to synthesize the simple manganese carbonyl fluorides arises from a lack of a suitable synthetic method rather than from the instability of the desired products.

Graphical abstract: Manganese carbonyl fluorides: are they viable molecules?

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Publication details

The article was received on 20 Feb 2012, accepted on 09 Mar 2012, published on 11 Apr 2012 and first published online on 11 Apr 2012


Article type: Paper
DOI: 10.1039/C2DT30405H
Citation: Dalton Trans., 2012,41, 6225-6231
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    Manganese carbonyl fluorides: are they viable molecules?

    J. Deng, Q. Li, Y. Xie and R. B. King, Dalton Trans., 2012, 41, 6225
    DOI: 10.1039/C2DT30405H

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