Synthesis and catalytic properties of cationic palladium(II) and rhodium(I) complexes bearing diphosphinidinecyclobutene ligands |
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| Affiliation: | 1. International Research Center for Elements Science (IRCELS), Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan;2. Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan |
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| Abstract: | Cationic palladium(II) and rhodium(I) 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(MeCN)2(DPCB–Y)]X2 (X = OTf, BF4, BAr4 (Ar = 3,5-bis(trifluoromethyl)phenyl)) were prepared by the reactions of DPCB–Y with [Pd(MeCN)4]X2, 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(μ-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 carbamate to α,β-unsaturated ketones. |
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