Syntheses and characterizations of methylpalladium complexes bearing a biphenyl-based bulky phosphine ligand: Weak interactions suggested by NBO and QTAIM analyses

Isolation of chloro-bridged arylpalladium complexes, [Pd2Ar2(μ-Cl)2(PR3)2], in palladium catalyzed C–C cross coupling reaction of triarylbismuth with arylhalides

“…The PdeCl bond trans to the aryl group is longer than the one trans to the phosphine ligand, and is consistent with the aryl group exerting greater trans influence than the phosphine ligand. These distances are in accord with the binuclear organopalladium complexes [19,26,31]. The PdeC distances (2.00 Å) are significantly shorter than the binuclear chloro-bridged methylpalladium complexes, [Pd 2 Me 2 (m-Cl) 2 (L) 2 ] (L ¼ PR 3 , AsPr i 3 ) (2.029e2.100 Å) [14,26,29e31] but are comparable to halo-bridged complexes, [Pd 2 Ph 2 (m-I) 2 (PPh 3 ) 2 ] (Pd-C ¼ 1.993(1)Å) [22] and [Pd 2 (C 6 H 4 Bu np) 2 (m-Br) 2 (P-o-tol 3 ) 2 ] (Pd-C ¼ 2.02(1)Å) [23].…”

“…IR spectra were recorded as Nujol mulls between CsI plates on a Bomem MB-102 FT IR spectrometer. The 1 H, 31 To a dichloromethane (20 ml) solution of [Pd 2 Cl 2 (m-Cl) 2 (PEt 3 ) 2 ] (163 mg, 0.275 mmol), a benzene solution of Ph 3 Bi (122 mg, 0.277 mmol) was added with stirring under a nitrogen atmosphere. The reactants were stirred for 3 h and then filtered through a G-3 filtering unit.…”

Biaryl Phosphane Ligands in Palladium‐Catalyzed Amination

“…[121] Such interactions have been observed in a number of palladium-biaryl phosphine X-ray crystal structures [27][28][29][122][123][124][125] and even in an oxidative addition complex with methyl triflate. [126] Obtaining experimental information on the importance of these interactions in the reactive, catalytically active species has proven more difficult. [127] These species have been examined by DFT methods, however, which has served to underline the importance of the Pdarene interactions in intermediates in the catalytic cycle (Figure 4).…”

Biarylphosphanliganden in der palladiumkatalysierten Aminierung

“…[121] Derartige Wechselwirkungen waren in Röntgenkris-tallstrukturanalysen einer Reihe von Palladium-Biarylphosphan-Komplexen zu beobachten, [27][28][29][122][123][124][125] und sogar im Produkt einer oxidativen Addition von Methyltriflat. [126] Es erwies sich als schwieriger, experimentelle Informationen über solche Wechselwirkungen in den katalytisch aktiven Spezies zu erhalten, [127] DFT-Rechnungen hoben jedoch die Bedeutung der Palladium-Aren-Wechselwirkungen für die Zwischenstufen im Katalysezyklus hervor. [128,129] Diese Studien wiesen ferner darauf hin, dass der untere Ring die reduktive Eliminierung fördert.…”