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
This publication has 30 references indexed in Scilit:
- Ar−F Reductive Elimination from Palladium(II) RevisitedOrganometallics, 2007
- Facile Ar−CF3 Bond Formation at Pd. Strikingly Different Outcomes of Reductive Elimination from [(Ph3P)2Pd(CF3)Ph] and [(Xantphos)Pd(CF3)Ph]Journal of the American Chemical Society, 2006
- Palladium(II) and Palladium(0) Complexes of BINAP(O) (2-(Diphenylphosphino)-2‘-(diphenylphosphinyl)-1,1‘-binaphthyl)Organometallics, 2002
- Is Fluoride Bonded to Two Pd Acceptors Still Basic? Three CH2Cl2 Molecules Encapsulating a Pd2(μ-F)2 Square and New Implications for CatalysisAngewandte Chemie-International Edition, 2002
- Palladium Fluoride Complexes: One More Step toward Metal-Mediated C−F Bond Formation Frontispiece shows woodcuts from: John French, The Art of Distillation, London, 1651. Courtesy of Adam McLean (http://www.levity.com/alchemy/).Chemistry – A European Journal, 2002
- Thermal Stability, Decomposition Paths, and Ph/Ph Exchange Reactions of [(Ph3P)2Pd(Ph)X] (X = I, Br, Cl, F, and HF2)Organometallics, 2000
- Low Valent Transition Metal FluoridesPublished by Elsevier BV ,2000
- Organometallic Fluorides: Compounds Containing Carbon−Metal−Fluorine Fragments of d-Block MetalsChemical Reviews, 1997
- Transition-metal fluoro compounds containing carbonyl, phosphine, arsine, and stibine ligandsChemical Reviews, 1991
- Why Are There No Terminal Oxo Complexes of the Late Transition Metals? or The Importance of Metal–Ligand π Antibonding InteractionsComments on Inorganic Chemistry, 1988