Abstract: In the present work, we have prepared a series of octahedral Fe(II) complexes of the type -[Fe(PNP)(CO)Cl]-PNP are tridentate pincer-type ligands based on 2,6-diaminopyridine. These complexes are formed irrespective of the size of the substituents at the phosphorus sites and whether -[Fe(PNP)(Cl)(CO)] or -[Fe(PNP)(Cl)(CO)] are reacted with CO in the presence of 1 equiv of silver salts. X-ray structures of representative complexes are presented. Based on simple bonding considerations the selective formation of -dicarbonyl Fe(II) complexes is unexpected. In fact, DFT calculations confirm that -dicarbonyl complexes are indeed thermodynamically disfavored over the respective -dicarbonyl compounds, but are favored for kinetic reasons.
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| http://dx.doi.org/10.1007/s00706-016-1811-x | DOI Listing |
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