Ir(III)-Induced C-Bound to N-Bound Tautomerization of a N-Heterocyclic Carbene

An iridium N-heterocyclic carbene (NHC) complex with a rare hydrogen wing tip was obtained via C−N bond cleavage. The C-bound to N-bound tautomerization of this carbene cannot be achieved in this neutral 18-electron Ir(III) complex. Chloride abstraction in MeCN afforded an NHC−acetimidamide complex, where the N-bound to C-bound tautomerization of this carbene was observed in CDCl3 at 110 °C. Crystal structures of iridium complexes with these rare ligands were reported

Ir(III)-Induced C-Bound to N-Bound Tautomerization of a N-Heterocyclic Carbene

An iridium N-heterocyclic carbene (NHC) complex with a rare hydrogen wing tip was obtained via C−N bond cleavage. The C-bound to N-bound tautomerization of this carbene cannot be achieved in this neutral 18-electron Ir(III) complex. Chloride abstraction in MeCN afforded an NHC−acetimidamide complex, where the N-bound to C-bound tautomerization of this carbene was observed in CDCl3 at 110 °C. Crystal structures of iridium complexes with these rare ligands were reported

Ir(III)-Induced C-Bound to N-Bound Tautomerization of a N-Heterocyclic Carbene

An iridium N-heterocyclic carbene (NHC) complex with a rare hydrogen wing tip was obtained via C−N bond cleavage. The C-bound to N-bound tautomerization of this carbene cannot be achieved in this neutral 18-electron Ir(III) complex. Chloride abstraction in MeCN afforded an NHC−acetimidamide complex, where the N-bound to C-bound tautomerization of this carbene was observed in CDCl3 at 110 °C. Crystal structures of iridium complexes with these rare ligands were reported

Iridium Abnormal N-Heterocyclic Carbene Hydrides via Highly Selective C−H Activation

Imidazoliums with proximal phosphines undergo C−H oxidative addition on [Ir(COD)Cl]2 to give iridium(III) abnormal carbene hydrides. The effects of the length of the linker between the imidazolium and the phosphine are systematically studied. These C−H activation products can undergo base-promoted H−Cl reductive elimination to afford the corresponding Ir(I) abnormal NHC complexes

Iridium Abnormal N-Heterocyclic Carbene Hydrides via Highly Selective C−H Activation

Imidazoliums with proximal phosphines undergo C−H oxidative addition on [Ir(COD)Cl]2 to give iridium(III) abnormal carbene hydrides. The effects of the length of the linker between the imidazolium and the phosphine are systematically studied. These C−H activation products can undergo base-promoted H−Cl reductive elimination to afford the corresponding Ir(I) abnormal NHC complexes

Iridium Abnormal N-Heterocyclic Carbene Hydrides via Highly Selective C−H Activation

Imidazoliums with proximal phosphines undergo C−H oxidative addition on [Ir(COD)Cl]2 to give iridium(III) abnormal carbene hydrides. The effects of the length of the linker between the imidazolium and the phosphine are systematically studied. These C−H activation products can undergo base-promoted H−Cl reductive elimination to afford the corresponding Ir(I) abnormal NHC complexes

Solid-State Structures of Double-Long-Chain Imidazolium Ionic Liquids: Influence of Anion Shape on Cation Geometry and Crystal Packing

The syntheses and solid-state structures of a series of imidazolium (IM) salt-based, double C12 alkyl chain functionalized ionic liquids, namely, [C12C12IM][A], where the anion A is I−, I3−, I5−, N(CN)2−, C(CN)3−, B(CN)4−, or SbF6−, are reported. All compounds were fully characterized by CHN elemental analysis, 1H and 13C NMR spectroscopy, and X-ray diffraction studies on single crystals. The molecular structure of the IM [C12C12IM]+ cation, as found in the individual crystal packing arrangements, is discussed in relation to the different anions used for crystallization. Depending on the geometry of the counteranions used (linear, bent, planar, and spherical), different molecular structures of the IM cations (rod-, V-, and U-shaped) resulted. The crystal packing in the solid-state structure is examined on the basis of a Hirshfeld surface analysis and is discussed in terms of polar and nonpolar regions

Solid-State Structures of Double-Long-Chain Imidazolium Ionic Liquids: Influence of Anion Shape on Cation Geometry and Crystal Packing

The syntheses and solid-state structures of a series of imidazolium (IM) salt-based, double C12 alkyl chain functionalized ionic liquids, namely, [C12C12IM][A], where the anion A is I−, I3−, I5−, N(CN)2−, C(CN)3−, B(CN)4−, or SbF6−, are reported. All compounds were fully characterized by CHN elemental analysis, 1H and 13C NMR spectroscopy, and X-ray diffraction studies on single crystals. The molecular structure of the IM [C12C12IM]+ cation, as found in the individual crystal packing arrangements, is discussed in relation to the different anions used for crystallization. Depending on the geometry of the counteranions used (linear, bent, planar, and spherical), different molecular structures of the IM cations (rod-, V-, and U-shaped) resulted. The crystal packing in the solid-state structure is examined on the basis of a Hirshfeld surface analysis and is discussed in terms of polar and nonpolar regions

Highly Luminescent Salts Containing Well-Shielded Lanthanide-Centered Complex Anions and Bulky Imidazolium Countercations

Four salts containing imidazolium cations and europium­(III)- or terbium­(III)-centered complex anions have been successfully synthesized from an ethanol/H₂O solution. The single-crystal X-ray diffraction analyses reveal that these compounds have a common formula of [R]­[Ln­(DETCAP)₄] [R = 1-ethyl-3-methylimidazolium (C₂mim), Ln = Eu (<b>1</b>) and Tb (<b>2</b>); R = 1-butyl-3-methylimidazolium (C₄mim), Ln = Eu (<b>3</b>) and Tb (<b>4</b>); DETCAP = diethyl-2,2,2-trichloroacetylphosphoramidate], in which the lanthanide centers are chelated by four chelating pseudo-β-diketonate ligands (DETCAP)⁻, forming the respective complex anions. Their thermal behaviors and stabilities were also investigated to study the role of the length of the side chain in the cations. Fluorescence measurements at both room temperature and liquid-nitrogen temperature show that these materials show intense characteristic europium­(III) or terbium­(III) emissions and have long decay times. Their overall quantum yields were determined to be in the range of 30–49%

Controlled Assembly of Eccentrically Encapsulated Gold Nanoparticles

Controlled Assembly of Eccentrically Encapsulated Gold Nanoparticle