478294-12-1Relevant academic research and scientific papers
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.
Disproportionation of PtPh(CH2COMe)(cod) and conproportionation of PtPh2(cod) and Pt(CH2COMe)2(cod) via intermolecular phenyl ligand transfer
Suzaki, Yuji,Yagyu, Takeyoshi,Yamamura, Yuichi,Mori, Atsunori,Osakada, Kohtaro
, p. 5254 - 5258 (2008/10/08)
PtI(Ph)(cod) (cod = 1,5-cyclooctadiene) reacts with acetone in the presence of Ag2O to give a mixture of Pt(CH2COMe)(Ph)(cod) (1), PtPh2(cod) (2), and Pt(CH2COMe)2(cod) (3) in a molar ratio of 61:20:19. Complex 1, having the phenyl and acetonyl ligands, was isolated by recrystallization of the products and characterized by X-ray crystallography. The reaction of AgBF4 with PtI(Ph)(cod) forms [PtPh(cod)(acetone-d6)]BF4 and does not give a diarylplatinum complex. Thus, Ag2O, in the reaction of PtI(Ph)(cod) with acetone, promotes activation of both the Pt-I bond of PtI(Ph)(cod) and a C-H bond of acetone. Heating of 1 in acetone at 50 °C causes its partial disproportionation into 2 and 3 to give a mixture of the above three complexes. An equimolar mixture of 2 and 3 in acetone undergoes conproportionation into 1 at 50 °C to give a mixture of the complexes. The conproportionation is completed in 30 h to form the mixture with [1]:[2]:[3] = 66:17:17, while the above disproportionation of 1 does not attain equilibrium even after 70 h. The disproportionation and conproportionation of these complexes are observed also in benzene at 50 °C.
