Gold(I) complexes of sterically demanding phosphines derived from 2,6-dibenzhydryl-4-methylphenyl core viz: 2,6-dibenzhydryl-N,N-bis((diphenylphosphane)-methyl)-4-methylaniline (1), (2,6-dibenzhydryl-4-methylphenyl)-diphenylphosphane (2), N-(2,6-dibenzhydryl-4-methylphenyl)-1,1-diphenylphosphanamine (3), and (2,6-dibenzhydryl-4-methylphenoxy)diphenylphosphane (4) are described. The reaction of 1 with 2 equiv of [AuCl(SMe 2 )] in dichloromethane yielded [{AuCl} 2 {Ar*N(CH 2 PPh 2 ) 2 }] (5), which on further treatment with 2 equiv of AgSbF 6 and 1 equiv ofEquimolar reactions of bulky phosphines 2, 3, and 4 with [AuCl(SMe 2 )] resulted in [AuCl(PPh 2 Ar*)] (8), [AuCl(PPh 2 NHAr*)] (9), and [AuCl(PPh 2 OAr*)] (10). Complexes 9 and 10 on treatment with AgSbF 6 in CH 3 CN produced the cationic complexes [Au(NCCH 3 )(PPh 2 NHAr*)][(SbF 6 )] (11) and [Au(NCCH 3 )(PPh 2 OAr*)][(SbF 6 )] ( 12), respectively. The molecular structure of complex 6 revealed the presence of a strong intramolecular aurophilic interaction with a Au•••Au distance of 2.9720(4) Å. Careful analysis of molecular structure of 5 revealed the presence of rare Au•••H−C (sp 3 ) interactions between the gold(I) atom and one of the methylene protons of −NCH 2 PPh 2 groups. The solution 1 H NMR signals of the methylene protons of 5 showed a considerable downfield shift (∼1 ppm) compared to that of the free ligand indicating their interactions (Au•••H) with the Au atom. Complexes 8 and 10 also showed Au•••H interactions in their molecular structures. The existence of the Au•••H interaction was studied by variable temperature 1 H NMR data in the case of complex 5 and further evinced by the QTAIM analysis in complexes 5, 8, and 10.
The synthesis and structural studies of palladium(II) complexes of sterically demanding mono‐phosphine Ar*PPh2 (1) (Ar*=2,6‐dibenzhydryl‐4‐methylphenyl) are described. The reactions of 1 with [Pd(COD)Cl2] and [Pd(η3‐C3H5)Cl]2 in 2 : 1 molar ratios afforded mononuclear complexes trans‐[PdCl2{(PPh2Ar*)‐κ1‐P}2] (2) and [Pd(η3‐C3H5)Cl{(PPh2Ar*)‐κ1‐P}] (3), respectively. Both the complexes have been fully characterized through NMR spectroscopy, elemental analyses, and single‐crystal X‐ray analysis. The molecular structures of 2 and 3 showed C−H⋅⋅⋅π interactions between methine hydrogen of one of the Ph2CH groups with the centroid of one of the phenyl rings of the PPh2 group. Complex 2 also showed intramolecular π⋅⋅⋅π stacking interactions between the phenyl rings of Ph2CH and PPh2 groups. In addition, complex 2 also showed C−H⋅⋅⋅Pd anagostic interaction between the methine hydrogen of one of the Ph2CH groups and the palladium center. The palladium complex 2 is found to be an efficient catalyst for the direct C‐5 arylation of imidazole derivatives under aerobic conditions.
This manuscript describes the syntheses of pyridine appended triazole-based mono- and bisphosphines, [o-Ph2P(C6H4){1,2,3-N3C(Py)C(H)}] (2), [o-Br(C6H4){1,2,3-N3C(Py)C(PPh2)}] (3), [C6H5{1,2,3-N3C(Py)C(PPh2)}] (4), Ph2P(C6H4){1,2,3-N3C(Py)C(PPh2)}] (5) and [3-Ph2P-2-{1,2,3-N3C(Ph)C(PPh2)}C5H3N] (6), their palladium, platinum chemistry and catalytic applications....
The synthesis of two new 1,2,3–triazole appended monophosphines [P(Ph){(o-C6H4)(1,2,3-N3C(Ph)CH}2] (1) and [P(Ph){o-C6H4(CCH)(1,2,3-N3-Ph)}2] (2) and their RuII complexes is described. The reactions of 1 and 2 with [Ru(PPh3)3Cl2] in 1:1 molar...
This paper describes the synthesis and the copper(i), silver(i) and gold(i) complexes of a novel large bite angle bisphosphine {(C6H4(PhC2N3)PiPr2)2-p}.
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