Rate and Mechanism of the Oxidative Addition of a Silylborane to Pt0 Complexes : Mechanism for the Pt-Catalyzed Silaboration of 1,3-Cyclohexadiene

• The chemical reduction of Pt(acac)(2) by DIBALH in the presence of phosphanes, which is used to generate active Pt-0 complexes in the Pt-catalyzed silaboration of cyclohexadiene by 2-(diinethylphenylsilyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1) leading to the 1,4-silaborated product, was mimicked by the electrochemical reduction of Pt(acac)(2) in the presence of 2 equiv. of PR3 (R = Ph, nBu). The electrochemical reduction generates free acac anions and neutral Pt-0-(PR3)(2) complexes. The kinetics of the oxidative addition of bromobenzene (used first as a model molecule) and silylborane 1 to the Pt-0 complexes was investigated and the rate constants determined. Pt-0(PnBu(3))(2) is much more reactive than Pt-0(PPh3)(2) towards 1. From the electrochemical study, it emerges that the acac anions released in the reduction of Pt(acac)(2) do not coordinate to the Pt-0(PR3)(2) complexes. Consequently, the rate of the oxidative addition of 1 to Pt-0(PR3)(2), generated either by the electrochemical reduction or by the chemical reduction by DIBALH, is not affected by the acac anions and a posteriori not by aluminum cations. The oxidative addition and the further step of the catalytic cycle [insertion of the diene into the Pt-B bond of the Si-Pt-B complex generated in the oxidative addition, with formation of the eta(3)-allyl)Pt-Si complex] were monitored by NMR spectroscopy. Pt-0 and Pt-II complexes involved in the catalytic cycle were characterized. The oxidative addition is faster when the ligand is PMe2Ph relative to that obtained with PPh3, in agreement with the electrochemical data. No reductive elimination within the ((eta(3)-allyl))Pt-Si complex is observed when the ligand is PMe2Ph, whereas reactions in the presence of PPh3 proceeded to give the final product. As a consequence, PPh3 is a better ligand than PMe2Ph for the catalytic reaction, as observed experimentally.

Subject headings

NATURVETENSKAP  -- Kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences (hsv//eng)

Keyword

Platinum; Silaboration; Reaction mechanisms; Kinetics

Chemistry

Kemi

Publication and Content Type

ref (subject category)

art (subject category)