Synthetic and computational studies of the palladium(IV) system Pd(alkyl)(aryl)(alkynyl)(bidentate)(triflate) exhibiting selectivity in C-C reductive elimination
Date
2012
Authors
Sharma, Manab
Ariafard, Alireza
Canty, Allan
Yates, Brian F
Gardiner, Michael G
Jones, Roderick C.
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Volume Title
Publisher
Royal Society of Chemistry
Abstract
Synthetic routes to methyl(aryl)alkynylpalladium(iv) motifs are presented, together with studies of selectivity in carbon-carbon coupling by reductive elimination from PdIV centres. The iodonium reagents IPh(CCR)(OTf) (R = SiMe3, But, OTf = O3SCF3) oxidise PdIIMe(p-Tol)(L2) (1-3) [L2 = 1,2-bis(dimethylphosphino)ethane (dmpe) (1), 2,2′-bipyridine (bpy) (2), 1,10-phenanthroline (phen) (3)] in acetone-d6 or toluene-d 9 at -80 °C to form complexes PdIV(OTf)Me(p-Tol)(CCR) (L2) [R = SiMe3, L2 = dmpe (4), bpy (5), phen (6); R = But, L2 = dmpe (7), bpy (8), phen (9)] which reductively eliminate predominantly (>90%) p-Tol-CCR above ∼-50 °C. NMR spectra show that isomeric mixtures are present for the PdIV complexes: three for dmpe complexes (4, 7), and two for bpy and phen complexes (5, 6, 8, 9), with reversible reduction in the number of isomers to two occurring between -80 °C and -60 °C observed for the dmpe complex 4 in toluene-d8. Kinetic data for reductive elimination from Pd IV(OTf)Me(p-Tol)(CCSiMe3)(dmpe) (4) yield similar activation parameters in acetone-d6 (66 ± 2 kJ mol -1, ΔH‡ 64 ± 2 kJ mol-1, ΔS‡ -67 ± 2 J K-1 mol-1) and toluene-d8 (Ea 68 ± 3 kJ mol-1, ΔH‡ 66 ± 3 kJ mol-1, ΔS ‡ -74 ± 3 J K-1 mol-1). The reaction rate in acetone-d6 is unaffected by addition of sodium triflate, indicative of reductive elimination without prior dissociation of triflate. DFT computational studies at the B97-D level show that the energy difference between the three isomers of 4 is small (12.6 kJ mol-1), and is similar to the energy difference encompassing the six potential transition state structures from these isomers leading to three feasible C-C coupling products (13.0 kJ mol-1). The calculations are supportive of reductive elimination occurring directly from two of the three NMR observed isomers of 4, involving lower activation energies to form p-TolCCSiMe 3 and earlier transition states than for other products, and involving coupling of carbon atoms with higher s character of σ-bonds (sp2 for p-Tol, sp for CC-SiMe3) to form the product with the strongest C-C bond energy of the potential coupling products. Reductive elimination occurs predominantly from the isomer with Me3SiCC trans to OTf. Crystal structure analyses are presented for PdIIMe(p-Tol) (dmpe) (1), PdIIMe(p-Tol)(bpy) (2), and the acetonyl complex Pd IIMe(CH2COMe)(bpy) (11).
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Keywords
Keywords: 1 ,10-phenanthroline; Activation parameter; Alkynyls; Bipyridines; C-C bonds; C-C coupling; Carbon atoms; Carbon-carbon coupling; Computational studies; Coupling product; Crystal structure analysis; Energy differences; Iodonium; Isomeric mixtures; Kinetic
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Dalton Transactions
Type
Journal article
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