Ruthenium Complexes with N-Bound 2-Pyridonato Ligand as O-Donors: A New Synthetic Approach and the Effect on Reactivity.

In this study, Ru complexes [(η6-p-cymene)RuX(2-{(2,6-iPr2-C6H3)N=CH}-C5H3N-6-(O))] (3: X=Cl; 4: X=I) were prepared with N-bound 2-pyridonato ligand by thermal base-free MeX elimination from ionic N,N-chelated Ru complexes [(η6-p-cymene)RuX(κ2-L1)](X) (1: X=Cl; 2: X=I; L1={2-[(2,6-iPr2-C6H3)N=CH]-6-(OMe)C5H3N}). The Ru complex 3 was used as O-donor for Lewis (LA) or Brönsted acids. The reactions of 3 with SnCl2, Ph3SnCl, ZnCl2 or HCl provided [(η6-p-cymene)Ru(SnCl3)(2-{(2,6-iPr2-C6H3)N=CH}-C5H3N-6-(O→SnCl2)] (6), [(η6-p-cymene)RuCl(2-{(2,6-iPr2-C6H3)N=CH}-C5H3N-6-(O→SnPh3Cl)] (7), and [(η6-p-cymene)RuCl(2-{(2,6-iPr2-C6H3)N=CH}-C5H3N-6-(O→)]2(µ-ZnCl2) (8) and [(η6-p-cymene)RuCl(2-{(2,6-iPr2-C6H3)N=CH}-C5H3N-6-(OH)}](Cl) (9). The easy conversion of the 2-pyridonato ligand in 3 to its 2-hydroxypyridine in 9 evoked testing of 3 and 4 as potential catalysts in base-free transfer-hydrogenation of ketones.

N-Coordinated tellurenium(II) and telluronium(IV) cations: synthesis, structure and hydrolysis.

A set of N-coordinated tellurium(II) compounds containing either C,N-chelating ligands CNR (where CN = 2-(RNCH)C6H4, R = tBu or Dipp; Dipp = 2,6-iPr2C6H3) or N,C,N pincer ligands NCNR (where NCN = 2,6-(RNCH)2C6H4, R = tBu or Dipp) were synthesized. In the case of C,N-chelated compounds, the reaction of CNDippLi with Te(dtc)2 (where dtc = Et2NCS2) in a 1 : 1 molar ratio smoothly provided the carbamate CNDippTe(dtc) which upon treatment with 2 eq. of HCl provided the chloride CNDippTeCl. In contrast, the analogous conversion of NCNRLi with Te(dtc)2 surprisingly furnished ionic bromides [NCNRTe]Br as a result of the exchange of dtc by Br coming from nBuBr present in the reaction mixture. Furthermore, the reaction of CNDippTeCl or [NCNRTe]Br with silver salts AgX (X = OTf or SbF6) provided the expected tellurenium cations [CNDippTe]SbF6 and [NCNRTe]X. To further increase the Lewis acidity of the central atom, the oxidation of selected compounds with 1 eq. of SO2Cl2 was examined yielding stable compounds [CNtBuTeCl2]X and [NCNtBuTeCl2]X. The oxidation of the Dipp substituted compounds proved to be more challenging and an excess of SO2Cl2 was necessary to obtain the oxidized products [CNDippTeCl2]SbF6 and [NCNDippTeCl2]SbF6, which could solely be characterized in solution. Compounds [CNtBuTeCl2]OTf and [NCNtBuTeCl2]OTf were shown to undergo a controlled hydrolysis to the corresponding telluroxanes. All compounds were studied by multinuclear NMR spectroscopy in solution and for selected compounds solid state 125Te NMR spectroscopy and single-crystal X-ray diffraction analysis were performed. The Lewis acidity of the studied cations was examined by the Gutmann-Beckett method using Et3PO as the probing agent. The Te-N chalcogen bonding situation of selected compounds has also been examined computationally by a set of real-space bonding indicators.

Sn,P-coordinated Ru cation: a robust catalyst for aerobic oxidations of benzylamine and benzyl alcohol.

A stable ionic κ2Sn,P-coordinated Ru complex shows excellent catalytic activity in aerobic oxidations of benzylamine and benzyl alcohol. This complex is stabilized by a stannylene-phosphine peri-substituted naphthalene ligand, which can act as either a reducing agent for a Ru(III) complex or as a κ2Sn,P-chelating ligand for Ru(II) compounds.

Organogermanium(II) Hydrides as a Source of Highly Soluble LiH.

The reactions of monomeric C,N-chelated organogermanium(II) hydride L(H)Ge⋅BH3 with organolithium salts RLi yielded lithium hydrogermanatoborates (Li(THF)2 {BH3 [L(H)GeR]})2 . Compound (Li(THF)2 {BH3 [L(H)GePh]})2 was used as a source of LiH for the reduction of organic C=O or C=N bonds in nonpolar solvents accompanied by the elimination of a neutral complex L(Ph)Ge⋅BH3 . The interaction of (Li(THF)2 {BH3 [L(H)GePh]})2 with the polar C=O bond was further investigated by computational studies revealing a plausible geometry of a pre-reactive intermediate. The experimental and theoretical studies suggest that, although the Li atom of (Li(THF)2 {BH3 [L(H)GePh]})2 coordinates the C=O bond, the GeH fragment is the active species in the reduction reaction. Finally, benzaldehyde was reduced by a mixture of L(H)Ge⋅BH3 with PhLi in nonpolar solvents.

Photophysical and Protonation Time Resolved Studies of Donor-Acceptor Branched Systems With Pyridine Acceptors.

A comparative study of the photophysical properties of octupolar pyridyl-terminated triphenylamine molecule, with its quadrupolar and dipolar analogues, by means of ambient and low temperature steady state spectroscopy and femtosecond to nanosecond time-resolved fluorescence spectroscopy is reported. The push-pull molecules bear triphenylamine electron donating core, pyridine peripheral electron acceptors, and acetylene π-bridge. The samples were studied in solvents of varying polarity and also upon addition of small amounts of acetic acid to induce protonation of the pyridine group. All samples exhibit significant positive fluorescence solvatochromism as well as a relaxation of their excited state to a solvent relaxed intramolecular charge transfer state on the picosecond time scale. For the octupolar compound, excited state relaxation occurs simultaneously with excitation energy hopping among the branches. The hopping time is solvent polarity controlled since it becomes slower as the polarity increases. The experimental hopping times are compared to those predicted by Förster and Fermi formulations. The samples are capable of emitting broadband light covering almost the whole visible spectrum by careful control of protonation. Energy transfer from the neutral toward the protonated species on the 1 ps time scale is revealed.

Alphabet-Inspired Design of (Hetero)Aromatic Push-Pull Chromophores.

Push-pull molecules represent a unique and fascinating class of organic π-conjugated materials. Herein, we provide a summary of their recent extraordinary design inspired by letters of the alphabet, especially focusing on H-, L-, T-, V-, X-, and Y-shaped molecules. Representative structures from each class were presented and their fundamental properties and prospective applications were discussed. In particular, emphasis is given to molecules recently prepared in our laboratory with T-, X-, and Y-shaped arrangements based on indan-1,3-dione, benzene, pyridine, pyrazine, imidazole, and triphenylamine. These push-pull molecules turned out to be very efficient charge-transfer chromophores with tunable properties suitable for second-order nonlinear optics, two-photon absorption, reversible pH-induced and photochromic switching, photocatalysis, and intercalation.