Synthesis of Functional Polyolefins Using Cationic Bisphosphine Monoxide–Palladium Complexes
作者:Brad P. Carrow、Kyoko Nozaki
DOI:10.1021/ja303507t
日期:2012.5.30
The copolymerization of ethylene with polar vinyl monomers, such as vinyl acetate, acrylonitrile, vinyl ethers, and allyl monomers, was accomplished using cationic palladium complexes ligated by a bisphosphine monoxide (BPMO). The copolymers formed by these catalysts have highly linear microstructures and a random distribution of polar functional groups throughout the polymer chain. Our data demonstrate that cationic palladium complexes can exhibit good activity for polymerizations of polar monomers, in contrast to cationic a-diimine palladium complexes (Brookhart-type) that are not applicable to industrially relevant polar monomers beyond acrylates. Additionally, the studies reported here point out that phosphine-sulfonate ligated palladium complexes are no longer the singular family of catalysts that can promote the reaction of ethylene with many polar vinyl monomers to form linear functional polyolefins.
The Di-<i>t</i>-Butylphosphinyl Directed <i>ortho</i> Metalation Group. Synthesis of Hindered Dialkylarylphosphines
作者:Matthew Gray、Brian J. Chapell、Jakob Felding、Nicholas J. Taylor、Victor Snieckus
DOI:10.1055/s-1998-1655
日期:1998.4
Using the new P(O) t Bu2 Directed Metalation Group, a variety of ortho-substituted aryl di-t-butylphenylphosphine oxides (2a-k) have been prepared, its relative metalation ability has been established, and reduction and homocoupling products (Scheme 4) have been obtained.
利用新的 P(O) t Bu2 定向金属化基团,制备了多种正交取代芳基二叔丁基苯基膦氧化物(2a-k),确定了其相对金属化能力,并获得了还原和均偶产物(方案 4)。