Abstract
The halostibine complexes [CpFe(CO)2(SbMe2Br)][CF3SO3] and [CpFe(CO)2(SbMe2Br)][BF4] both contain significant interactions between the anion and the formally neutral Sb(III) ligand, which simultaneously displays Lewis acidic and Lewis basic properties. The unexpected secondary product [CpFe(CO)(Me2BrSb-μ-Br-SbBrMe2)] is formed in the presence of excess ligand, the strongly associated Br– anion bridging the two Sb donors to form a four-membered FeSb2Br ring.
Highlights
Transition-metal complexes with heavy main-group ligands have been a focus of recent interest due to the propensity of the coordinated heavy p-block donor atom to undergo further bonding interactions or even redox chemistry.[1−4] Gabbaıand co-workers have classed this as “coordination noninnocence” and have exploited such behavior for selective F− sensing.[3]
We have reported Mn(I) carbonyl complexes of halostibines in which the coordinated Sb donor atom acts as an acceptor, forming interactions with nearby [CF3SO3]− anions which significantly distort the geometry of the Sb center.[10]
The crystal structure of the [CF3SO3]− salt shows disorder of the whole structure, which was successfully modeled in two parts for both the cation and the anion (Figure 1 shows one part of each)
Summary
Transition-metal complexes with heavy main-group ligands have been a focus of recent interest due to the propensity of the coordinated heavy p-block donor atom to undergo further bonding interactions or even redox chemistry.[1−4] Gabbaıand co-workers have classed this as “coordination noninnocence” and have exploited such behavior for selective F− sensing.[3]. These interactions are believed to be the driving force for the unexpected formation of the monocarbonyl adduct [CpFe(CO)(Me2BrSb-μ-Br-SbBrMe2)], in which Br− is strongly associated with both coordinated Sb atoms.
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