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A solvent effect was found in the hydrogenation of acetophenone catalyzed by a new Pd/S-DVB catalyst, immobilized on a styrene (S)/divinylbenzene (DVB) copolymer containing phosphinic groups. The porous structure of the catalyst was characterized by a specific surface area of 94.7 m2 g−1. The presence of Pd(II) and Pd(0) in Pd/S-DVB was evidenced by XPS and TEM. Pd/S-DVB catalyzes the hydrogenation of acetophenone (APh) to 1-phenylethanol (PhE) and ethylbenzene (EtB). The highest conversion of APh was obtained in methanol (MeOH) and in 2-propanol (2-PrOH), while in water it was lower. The conversion of APh correlates well with the hydrogen-bond-acceptance (HBA) capacity of the solvent. However, in all binary mixtures of alcohol and water the APh conversion and the yield of products significantly decreased. The observed inhibiting effect can be explained by the microheterogeneity of these mixtures and the blocking of the catalyst surface restricting access of the substrates to the Pd centers.

A new triphenolic hexaaza chiral macrocyclic amine L forms trinuclear complexes 1-3 with rare earth metal lanthanide(III) ions (Ln = Dy, Eu, and Y) with the general formula Ln(3)L(mu(3)-OH)(2)(NO3)(4)(H2O)(2)]center dot xCH(3)OH. The crystal structures of the nitrate derivatives of this type reveal the presence of a {Ln(3)(mu(3)-OH)(2)} core within the macrocycle. For the chloride derivative of dysprosium(III) 4, a duplex of the trinuclear compound is formed to give the hexanuclear Dy6L2(mu(3)-OH)(3)(mu-O)(2-Cl)(3)Cl-4(H2O)(2)] compound, in which two trinuclear macrocyclic units are linked by bridging chloride anions, supplemented by a hydrogen bond connecting the central oxo and hydroxo bridges as well as by weak interactions at the periphery of the macrocycle. The nuclear magnetic resonance spectra of these complexes reveal a dynamic behavior in solution related to exchange of axial ligands and hindered rotation of phenyl substituents. Magnetic studies of the nitrate (1-3) and chloride (4) dysprosium(III) complexes suggest the presence of weak ferromagnetic interactions between neighboring metal centers. The interaction is strongest for compound 1, and for the related duplex compound 4, it appears to be somewhat weaker. The ac susceptibility measurements for complexes 1 and 4 confirm their field-induced single-molecule magnet behavior with the following characteristics: Lie ff = 10.6 cm(-1) (15.2 K), ro = 2.05 X 10(-4) s under 2500 Oe dc fields for 1; Ue ff 7.9 cm-' (11.4 K), ao = 1.68 X 10(-4) s under a 3000 Oe dc field for 4.

Three zinc(II) ions in combination with two units of enantiopure [3+3] triphenolic Schiff-base macrocycles 1, 2, 3, or 4 form cage-like chiral complexes. The formation of these complexes is accompanied by the enantioselective self-recognition of chiral macrocyclic units. The X-ray crystal structures of these trinuclear complexes show hollow metal-organic molecules. In some crystal forms, these barrel-shaped complexes are arranged in a window-to-window fashion, which results in the formation of 1D channels and a combination of both intrinsic and extrinsic porosity. The microporous nature of the [Zn3 12 ] complex is reflected in its N2 , Ar, H2 , and CO2 adsorption properties. The N2 and Ar adsorption isotherms show pressure-gating behavior, which is without precedent for any noncovalent porous material. A comparison of the structures of the [Zn3 12 ] and [Zn3 32 ] complexes with that of the free macrocycle H3 1 reveals a striking structural similarity. In H3 1, two macrocyclic units are stitched together by hydrogen bonds to form a cage very similar to that formed by two macrocyclic units stitched together by Zn(II) ions. This structural similarity is manifested also by the gas adsorption properties of the free H3 1 macrocycle. Recrystallization of [Zn3 12 ] in the presence of racemic 2-butanol resulted in the enantioselective binding of (S)-2-butanol inside the cage through the coordination to one of the Zn(II) ions.

The template condensation of (1 R ,2 R )- or (1 S ,2 S )-1,2-diaminocyclohexane, N,N′-bis(3-aminopropyl)ethylenediamine and paraformaldehyde in the presence of zinc(II) chloride or copper(II) chloride, followed by the metathesis with hexafluorophosphate or tetraphenylborate, afforded chiral, enantiopure Zn(II) complexes ( R , R )-[ZnL 1 Cl](PF 6 ), ( S , S )-[ZnL 1 Cl](PF 6 ), ( R , R )-[ZnL 1 Cl](BPh 4 ) ( R , R )-[CuL 1 Cl](BPh 4 ) and ( S , S )-[CuL 1 Cl](BPh 4 ) of the chiral macrocyle L 1 (1,3,10,12,16,19-hexaazatetracyclo[17,3,1,1 12,16 ,0 4,9 ]tetracosane). Similar condensation of (1 R ,2 R )-1,2-diaminocyclohexane, N,N′-bis(2-aminoethyl)ethylenediamine and paraformaldehyde in the presence of zinc(II) chloride afforded the enantiopure complex ( R , R )-[ZnL 2 Cl](BPh 4 ) of the chiral macrocyle L 2 (1,3,10,12,15,18-hexaazatetracyclo[16,2,1,1 12,15 ,0 4,9 ]docosane). The complexes have been characterised on the basis of NMR, CD and ESI MS spectra and elemental analyses. In these complexes the chirality at the carbon atoms of the cyclohexyl fragment determines the chirality at the coordinated nitrogen atoms. The X-ray crystal structures of the ( R , R )-[ZnL 1 Cl](PF 6 ), ( R , R )-[ZnL 1 Cl](BPh 4 ) and ( R , R )-[CuL 1 Cl](BPh 4 ) complexes indicate the untypical for this class of complexes (R,S,R,S) configuration at the coordinated nitrogen atoms. The 1,3-diazacyclohexane rings fused to the two six-membered chelate rings are both bend towards the apical chloride anion. The 2D NMR spectra confirm the presence of single conformation of the complex present in acetone solution, in particular the ROESY spectrum confirms the characteristic bending of the 1,3-diazacyclohexane rings towards the same side of the macrocyle, observed in the crystal structure. On the other hand the crystal structure of the ( R , R )-[ZnL 2 Cl](BPh 4 ) complex indicate more common (R,R,S,S) configuration at the coordinated nitrogen atoms, accompanied by bending of the two fused 1,3-diazacyclopentane rings towards the opposite sides of the macrocycle.