trans-Difluoro Complexes of Palladium(II)
- 5 January 2009
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 131 (3) , 918-919
- https://doi.org/10.1021/ja808975a
Abstract
Complexes trans-[(Py)2Pd(Ph)(F)] (1; Py = pyridine) and trans-[(t-BuPy)2Pd(Ph)(F)] (2; t-BuPy = 4-tert-butylpyridine) have been prepared from the corresponding iodides and AgF. Thermal decomposition of 1 and 2 in anhydrous benzene at 80 °C did not result in C−F bond formation, but Pd black and Ph2 were produced instead, along with novel difluorides trans-[(Py)2Pd(F)2] (3) and trans-[(t-BuPy)2Pd(F)2] (4). Both 3 and 4, the first trans-difluoro d8 square complexes, were independently synthesized from the corresponding diiodides and AgF and fully characterized. Contrary to filled/filled dπ−pπ repulsion considerations, the Pd−F bond distances in 3 and 4 are unprecedentedly short, being only 1.947(4)−1.958(4) Å and shorter than those in 1 and 2 by 0.12−0.13 Å. The mechanism of formation of 3 and 4 and bonding in these complexes are discussed.Keywords
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