A Novel Family of Cage-like (CuLi, CuNa, CuK)-phenylsilsesquioxane Complexes with 8-Hydroxyquinoline Ligands: Synthesis, Structure, and Catalytic Activity.

The first examples of metallasilsesquioxane complexes, including ligands of the 8-hydroxyquinoline family 1-9, were synthesized, and their structures were established by single crystal X-ray diffraction using synchrotron radiation. Compounds 1-9 tend to form a type of sandwich-like cage of Cu4M2 nuclearity (M = Li, Na, K). Each complex includes two cisoid pentameric silsesquioxane ligands and two 8-hydroxyquinoline ligands. The latter coordinates the copper ions and corresponding alkaline metal ions (via the deprotonated oxygen site). A characteristic (size) of the alkaline metal ion and a variation of characteristics of nitrogen ligands (8-hydroxyquinoline vs. 5-chloro-8-hydroxyquinoline vs. 5,7-dibromo-8-hydroxyquinoline vs. 5,7-diiodo-8-hydroxyquinoline) are highly influential for the formation of the supramolecular structure of the complexes 3a, 5, and 7-9. The Cu6Na2-based compound 2 exhibits high catalytic activity towards the oxidation of (i) hydrocarbons by H2O2 activated with HNO3, and (ii) alcohols by tert-butyl hydroperoxide. Studies of kinetics and their selectivity has led us to conclude that it is the hydroxyl radicals that play a crucial role in this process.

Stereoisomerism as an Origin of Different Reactivities of Ir(III) PC(sp3)P Pincer Catalysts.

Two stereoisomers of pentacoordinate iridium(III) hydridochloride with triptycene-based PC(sp3)P pincer ligand (1,8-bis(diisopropylphosphino)triptycene), 1 and 2, differ by the orientation of hydride ligand relative to the bridgehead ring of triptycene. According to DFT/B3PW91/def2-TZVP calculations performed, an equatorial Cl ligand can relatively easily change its position in 1, whereas that is not the case in 2. Both complexes 1 and 2 readily bind the sixth ligand to protect the empty coordination site. Variable temperature spectroscopic (NMR, IR, and UV-visible) studies show the existence of two isomers of hexacoordinate complexes 1·MeCN, 2·MeCN, and 2·Py with acetonitrile or pyridine coordinated trans to hydride or trans to metalated C(sp3), whereas only the equatorial isomer is found for 1·Py. These complexes are stabilized by various intramolecular noncovalent C-H···Cl interactions that are affected by the rotation of isopropyls or pyridine. The substitution of MeCN by pyridine is slow yielding axial Py complexes as kinetic products and the equatorial Py complexes as thermodynamic products with faster reactions of 1·L. Ultimately, that explains the higher activity of 1 in the catalytic alkenes' isomerization observed for allylbenzene, 1-octene, and pent-4-enenitrile, which proceeds as an insertion/elimination sequence rather than through the allylic mechanism.

Interaction of a trinuclear copper(i) pyrazolate with alkynes and carbon-carbon triple bond activation.

The trinuclear copper(i) pyrazolate {[3,5-(CF3)2Pz]Cu}3 forms η2-copper/alkyne triple bond coordinated structures in the presence of acetylenes. There is no coordination of copper atoms to the phenyl ring of phenylacetylene and copper(i) acetylide formation during the interaction. It was observed that the complexes formed are the active catalytic species in click reactions.