Synthesis and catalytic properties of cationic palladium(II) and rhodium(I) complexes bearing diphosphinidinecyclobutene ligands
Synthesis and catalytic properties of cationic palladium(II) and rhodium(I) complexes bearing diphosphinidinecyclobutene ligands
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DOI：
10.1016/j.jorganchem.2006.04.048
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发表时间：
2007-01-01
影响因子：
2.3
通讯作者：
Yoshifuji, Masaaki
中科院分区：
文献类型：
--
作者：
Jensen, Rader S.;Umeda, Kazutoshi;Yoshifuji, Masaaki
合成了含1，2-二芳基-3，4-双[（2，4，6-三叔丁基苯基）亚膦基]环丁烯配体的阳离子钯（II）和铑（I）配合物（DPCB-Y），考察了它们的结构和催化活性（芳基=苯基（DPCB）、4-甲氧基苯基（DPCB-OMe）、4-三氟甲基苯基（DPCB-CF_3））。以Pd（Ac）（2）和HX为原料，在乙腈中反应生成[Pd（MeCN）（4）] X-2，再与DPCB-Y反应，合成了[Pd（McCN）（2）（DPCB-Y）] X-2（X = OTf，BF_4，BAr_4（Ar = 3，5-二（三氟甲基）苯基））。另一方面，铑配合物[Rh（MeCN）（2）（DPCB-Y）] OTf通过在CH 2Cl 2中用DPCB-Y处理[Rh（mu-Cl）（环辛烯）（2）]（2），然后在MeCN存在下用AgOTf处理来制备。阳离子配合物催化氨基甲酸苄酯与α，β-不饱和酮的共轭加成反应。(c)2006 Elsevier B.V.保留所有权利。
Cationic palladium(II) and rhodium(l) complexes bearing 1,2-diaryl-3,4-bis[(2,4,6-tri-t-butylphenyl)phosphinidene]cyclobutene ligands (DPCB-Y) were prepared and their structures and catalytic activity were examined (aryl = phenyl (DPCB), 4-methoxyphenyl (DPCB-OMe), 4-(trifluoromethyl)phenyl (DPCB-CF3)). The palladium complexes [Pd(McCN)(2)(DPCB-Y)]X-2 (X = OTf, BF4, BAr4 (Ar = 3,5-bis(trifluoromethyl)phenyt)) were prepared by the reactions of DPCB-Y with [Pd(MeCN)(4)]X-2, which were generated from Pd(OAc)(2) and HX in MeCN. On the other hand, the rhodium complexes [Rh(MeCN)(2)(DPCB-Y)]OTf were prepared by the treatment of [Rh(mu-Cl)(cyclooctene)(2)](2) with DPCB-Y in CH2Cl2, followed by treatment with AgOTf in the presence of MeCN. The cationic complexes catalyzed conjugate addition of benzyl carbarnate to alpha,beta-unsaturated ketones. (c) 2006 Elsevier B.V. All rights reserved.