A new, easily recyclable arylating agent based on a diphosphino-digold(i) complex

Abstract

The synthesis of two organogold(I) complexes, [(Au(NCN))2(dppbp)] (6) and [(Au(Phebox))2(dppbp)] (9), and their application in subsequent transmetalating reactions are described. A trinuclear organogold(I) complex, [(AuCl)3(tdpppb)] (4) is also reported, which exhibits a surprisingly high solubility in dichloromethane. It was found that 6 and 9 can cleanly transfer the anionic NCN-([C(6)H(3)(CH(2)NMe(2))2-2,6]-) or Phebox-([2,6-bis(oxazolinyl)phenyl]-) moiety to Ti(IV) and Pd(II) centers, respectively. The coproduct [(AuCl)2(dppbp)] (3, dppbp is [4-Ph(2)PC(6)H(4)]2 (1)) formed during this transmetalation reaction, precipitates almost quantitatively from the reaction mixture (toluene) and can thus be separated by simple filtration. In comparison, [AuCl(PPh3)], formed as the coproduct in the transmetalation reaction of [Au(NCN)(PPh3)] with metal salts, has a higher solubility in apolar solvents and thus is more difficult to separate from the resultant organometallic complex. Digold complex 6 has been characterized by NMR spectroscopy and crystallographic analyses. These analyses show that the two gold units are essentially independent. The formation of a dimetallic transmetalating agent based on gold(I) had no effect on its transmetalating properties.

A Cationic AgI(PNPtBu) Species Acting as PNP Transfer Agent: Facile Synthesis of Pd(PNPtBu)(alkyl) Complexes and Their Reactivity Compared to PCPtBu Analogues

“…To shed more light on this possibility, single crystals, grown by slow diffusion of hexane into a CH 2 Cl 2 solution, were subjected to an X-ray crystallographic analysis; the molecular structure is depicted in Figure . As anticipated, a nonlinear coordination of the Au I ion between the two phosphine groups of the PNP tBu ligand exists, with Au−P distances of ∼2.31−2.32 Å, which are in the range observed for Au-phosphine complexes . The pyridine N atoms are pointing away from the virtual metallo-based rectangle.…”

Hydrogenation of CO2 to Formate over Ruthenium Immobilized on Solid Molecular Phosphines

“…The solid‐state magic angle spinning (SS‐MAS) 13 C cross polarization (CP) NMR spectrum (Figure a) presents peaks in the aromatic range, which are assigned to the aromatic linker . Besides this, small peaks are observed in the aliphatic range.…”

Novel Trisphosphine Ligand Containing 1,3,5-Triazine Core, [2,4,6-C3N3{C6H4PPh2-p}3]: Synthesis and Transition Metal Chemistry

“…The 31 P{ 1 H} NMR spectrum of complex 6 exhibits a single resonance at 33.0 ppm. The synthesis of trisgold complex containing the analogous phenyl derivative 1,3,5-tris[4-(diphenylphosphino)phenyl]benzene has been reported . The gold complex 6 on treatment with 3 equiv of AgOTf, followed by the addition of 2,2′-bpy or 1,10-phen gave the corresponding substituted complexes, [{Au(2,2′-bpy)} 3 {2,4,6-C 3 N 3 (C 6 H 4 PPh 2 - p ) 3 }](OTf) 3 ( 7 ) and [{Au(1,10-phen)} 3 {2,4,6-C 3 N 3 -(C 6 H 4 PPh 2 - p ) 3 }](OTf) 3 ( 8 ) as white crystalline solids (Scheme ).…”

“…Therefore, it would be interesting to explore such systems in material applications , and also in homogeneous as well as heterogeneous catalysis. Although the similar trisphosphine, 1,3,5-C 3 N 3 (PPh 2 ) 3 ( VIII ), and its silver complexes − have been reported, the corresponding phenyl derivative, 1,3,5-C 6 H 3 -2,4,6-(C 6 H 4 PPh 2 - p ) 3 ( VII ), has been reported very recently . As an extension of our interest − and the interest of others ,, in highly symmetrical polyphosphanes, we have sought to prepare triazine-based trisphosphines to explore their coordination chemistry.…”