Abstract
The thermodynamics of halogen bonding of a series of isostructural Group 10 metal pincer fluoride complexes of the type [(3,5‐R2‐tBuPOCOPtBu)MF] (3,5‐R2‐tBuPOCOPtBu=κ 3‐C6HR2‐2,6‐(OPtBu2)2 with R=H, tBu, COOMe; M=Ni, Pd, Pt) and iodopentafluorobenzene was investigated. Based on NMR experiments at different temperatures, all complexes 1‐tBu (R=tBu, M=Ni), 2‐H (R=H, M=Pd), 2‐tBu (R=tBu, M=Pd), 2‐COOMe (R=COOMe, M=Pd) and 3‐tBu (R=tBu, M=Pt) form strong halogen bonds with Pd complexes showing significantly stronger binding to iodopentafluorobenzene. Structural and computational analysis of a model adduct of complex 2‐tBu with 1,4‐diiodotetrafluorobenzene as well as of structures of iodopentafluorobenzene in toluene solution shows that formation of a type I contact occurs.
Highlights
Halogen bonding (XB), a non-covalent interaction between electron-deficient halogen atoms and a Lewis-basic site, has attracted considerable attention in recent years due to its relevance for numerous applications including functional materials, supramolecular polymers, molecular recognition, anion receptors, crystal engineering, and organocatalysis.[1,2] Halogen bonding is a highly directional interaction that can be described using different models, one of them being the socalled s hole that results from an anisotropic electron distribution around halogen atoms when being covalently bound to a residue R
We present a combis(phosphine) complexes that form monofluorides upon CÀF parative study of halogen bonding of isostructural Group 10 activation of fluorinated aromatics such as hexafluorobenzene fluoride complexes with C6F5I in solution. and fluorinated pyridines (Figure 1)
We have studied halogen bonding of a series material with a NaH suspension, followed by filtration to yield of isostructural Group 10 pincer iodide complexes of the type the pure metal fluoride complexes
Summary
C6F4I2 was used before as a donor for structural studies of halogen bonding of palladium pincer complexes.[23] Co-crystallization of 2-tBu and C6F4I2 in 2:1 ratio from toluene yields the adduct 2-tBu·I-C6F4-I. In a previous structural study Whitwood, Brammer, and Perutz showed that the degree of bending of the MÀX···IÀC unit is strongly dependent on the halide X of the acceptor component with fluorides resulting in linear arrangements whereas structures of metal iodide adducts are bent significantly.[8e] Notably, XB interactions of electron deficient s holes with regions of higher electron density are typically strongly bent. Computed structural parameters for these adducts are in the same range as found before for related halogen bonding systems with Group 10 fluoride complexes.[11b]
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