899439-56-6Relevant articles and documents
Transmetalation of arylpalladium and platinum complexes. Mechanism and factors to control the reaction
Suzaki, Yuji,Yagyu, Takeyoshi,Osakada, Kohtaro
, p. 326 - 342 (2008/02/03)
This article reviews recent studies on intra- and intermolecular transfer of the aryl ligand bonded to Pd(II) and Pt(II). Cationic arylpalladium complexes with bpy and THF ligands undergo intermolecular aryl group transfer to produce biaryl via a diarylpalladium intermediate. This reaction is applied to cyclization of cationic dinuclear arylpalladium complexes, affording the crown ether derivative with biphenylene units. Analogous arylplatinum complexes do not form diaryl complexes via transmetalation, while they react with CO and phenylallene to cause replacement of the coordinated solvent and insertion of the small molecules into the Pt-C bond, respectively. Conproportionation of PtCl2(cod) and PtPh2(cod) produces PtCl(Ph)(cod), which is induced by dissociation of a Cl ligand from the former complex. PtCl2(cod) reacts also with diarylplatinum complexes with bpy and dppe. Disproportionation of PtPh(CH2COMe)(cod) and conproportionation of PtPh2(cod) and Pt(CH2COMe)2(cod) take place at 50 °C, but the rates of apparently reversible reactions differ from each other. Addition of OH- to a solution of PtI(Ph)(cod) causes intermolecular phenyl ligand transfer to produce PtPh2(cod). The dinuclear intermediate complex with bridging OH ligand is prepared from an independent route and fully characterized. The complex causes transmetalation of aryl group of aryl boronic acid.
Chemical properties of mononuclear and dinuclear phenylplatinum(II) hydroxo complexes with cod ligands. Transmetalation of arylboronic acids, coupling of the phenyl ligands, and carbonylation
Suzaki, Yuji,Osakada, Kohtaro
, p. 3251 - 3258 (2008/10/09)
The reaction of bpy with [{Pt(Ph)(cod)}2(μ-OH)](BF 4) (1-BF4; cod = 1,5-cyclooctadiene) in acetone splits a Pt-O bond to yield a mixture of Pt(CH2COMe)(Ph)(cod) (2) and [Pt(Ph)(bpy)(cod)](BF4) (3-BF4), whereas a similar reaction in toluene produces 3-BF4 and Pt(OH)(Ph)(cod) (4). The complex 4 was obtained in solution and was not isolated as analytically pure crystals because of its gradual disproportionation, giving PtPh2(cod) (5). The dinuclear complex 1-BF4 reacts with ArB(OH)2 (Ar = Ph, C6H2F3-2,4,6) to form 5 and Pt(C 6H2F3-2,4,6)(Ph)(cod) (6), respectively, via aryl group transfer from boron to platinum. The accompanying formation of B(OH)3 has been confirmed by 11B{1H} NMR spectroscopy. The reaction of BF3·Et2O with 1-BF4 followed by the addition of NH4Cl(aq) produces biphenyl and PtCl2(cod), which takes place possibly via a dinuclear intermediate. The cationic dinuclear complex 1-BF4 reacts with CO (1 atm) to form benzophenone. Since the reactions of AgBF4 with Pt-(COPh)(I)(cod) (7) and CO with [Pt(Ph)(THF)(cod)](BF4) also yield benzophenone, the above carbonylation of 1-BF4 is considered to involve mononuclear intermediates.