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Issue 4, 2011
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Exchange coupling through diamagnetic [Fe(CO)4]2 bridging ligands in a xenophilic cluster

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Abstract

The electronic structure of so-called ‘xenophilic’ clusters, which contain both organometallic fragments and Werner-type paramagnetic transition metal centres, presents a challenge to simple theories of bonding. Density functional theory shows clearly that the cluster Mn2(thf)4(Fe(CO)4)2 is best described as an exchange-coupled MnII2 dimer, the closed-shell organometallic [Fe(CO)4]2 fragments acting simply as bridging ligands. The high-spin configuration of the MnII ions leads to single occupation of the Mn–Fe σ* orbitals and therefore substantially weaker metal–metal bonding than in conventional low-valent organometallic clusters. The transition metal fragments are effective mediators of superexchange (Jcalc = −44 cm−1), leading to the measured effective magnetic moment of ∼5 μB at 300 K, considerably lower than the limiting value of 8.37 μB for two uncoupled S = 5/2 MnII centres.

Graphical abstract: Exchange coupling through diamagnetic [Fe(CO)4]2− bridging ligands in a xenophilic cluster

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Publication details

The article was received on 13 Sep 2010, accepted on 18 Nov 2010 and first published on 10 Dec 2010


Article type: Paper
DOI: 10.1039/C0DT01221A
Citation: Dalton Trans., 2011,40, 927-932
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    Exchange coupling through diamagnetic [Fe(CO)4]2 bridging ligands in a xenophilic cluster

    T. Krämer, Z. Lin and J. E. McGrady, Dalton Trans., 2011, 40, 927
    DOI: 10.1039/C0DT01221A

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