Axially chiral monomeric and dimeric square planar Pd(II) complexes and their application to chiral tectonics

作者：Sato Hisako^*; Morimoto Kazuya; Mori Yukie; Shinagawa Yuji; Kitazawa Takafumi; Yamagishi Akihiko

来源：Dalton Transactions, 2013, 42(21): 7579-7585.

DOI：10.1039/c3dt50420d

Mononuclear and dinuclear square planar palladium(II) complexes (denoted by [(hfac)Pd(II)(L-LH)] and [(hfac)Pd(II)(L-L)Pd(II)(hfac)], respectively) were synthesized. Here hfac(-), HL-L- and L-L2- denote hexafluoroacetylacetonato, monoprotonated and non-protonated bis-beta-diketonato ligands, respectively. Three bis-beta-diketones were used as HL-LH: 1,2-diacetyl-1,2-dibenzoylethane (denoted by dabeH(2)), 1,2-diacetyl-1,2-bis(3-methylbutanoyl)ethane (baetH(2)) and 1,2-diacetyl-1,2-propanoylethane (dpeH(2)). Both the monomeric and dimeric Pd(II) complexes were chiral due to the orthogonal twisting of the two non-symmetric diketonato moieties in HL-L- and L-L2-, respectively. Optical resolution of [(hfac)Pd(II)(dabe)Pd(II)(hfac)] was achieved chromatographically on a chiral column to obtain a pair of optical antipodes which were stable against racemization. As for the other complexes, resolution was possible only after replacing hfac(-) with a bulky ligand such as dibenzoylmethanato (dbm(-)). Although a dinuclear complex with a symmetric bis-beta-diketonato ligand, [(hfac)Pd(II)(taet)Pd(II)(hfac)] (taet(2-) = 1,1,2,2-tetraacetylethanato), was achiral, the replacement of the terminal ligands with non-symmetric beta-diketonates yielded an axially chiral complex such as [(phacac)Pd(II)(taet)Pd(II)(phacac)], wherein phacac(-) denotes 1-phenyl-1,3-butanedionato. The UV and CD spectra of the Pd(II) complexes were analyzed with the help of the TDDFT calculations. The chiral monomeric species, [(dbm)Pd(II)(R- or S-baetH)], formed a heterometallic tetranuclear complex, [Fe(III){(dbm)Pd(II)(R- or S-baet)}(3)], in methanol solution.

• 出版日期2013