Reactivity of a new aryl cycloplatinated(ii) complex containing rollover 2,2′-bipyridine:<i>N</i> -oxide toward a series of diphosphine ligands

A new rollover cycloplatinated(ii) complex was prepared. The reactivity of this complex was investigated towards a wide range of diphosphine ligands.</p

A synthesis of thioxo[3.3.3]propellanes from acenaphthoquinone-malononitrile adduct, primary amines and CS2 in water

Novel thioxo[3.3.3]propellanes were synthesized in moderate to good yields via reactions of aromatic or aliphatic amines and carbon disulfide with the Knoevenagel adduct resulting from acenaphthoquinone and malononitrile in water at room temperature. The merit of this reaction is highlighted by its high atom-economy, chemo-selectivity, and lack of metal promoters. The structures of the products were established by IR, NMR, and single crystal X-ray analyses

Isolation of a 2‑Hydroxytetrahydrofuran Complex from Copper-Promoted Hydroxylation of THF

A complex of a binucleating macrocyclic ligand comprising a [Cu^II(μ-OH)­Na]²⁺ core reacts with CuI in THF/CH₃CN to yield a novel species with a deprotonated 2-hydroxytetrahydrofuran (THF-2-ol) bridging between Cu^II and Na^I ions. The complexes were characterized by X-ray crystallography, electron paramagnetic resonance spectroscopy, and electrospray ionization mass spectrometry. ¹⁸O-labeling studies support incorporation of the O atom from μ-OH into the coordinated THF-2-ol ligand

Copper‑, Palladium‑, and Platinum-Containing Complexes of an Asymmetric Dinucleating Ligand

The coordination chemistry of an asymmetric dinucleating hexadentate ligand LH₂ comprising neutral alkyltriamine and potentially dianionic dicarboxamido-pyridyl donor sets with copper, palladium, and platinum has been explored. Monometallic, dicopper, and heterodinuclear Cu–Pd and −Pt complexes have been prepared and characterized, including by NMR, EPR, UV–vis, and IR spectroscopy and X-ray crystallography. For example, the monometallic complexes [(LH₂)­MCl]­X (M = Cu, X = OTf; M = Pd or Pt, X = Cl) were prepared, wherein the metal­(II) ions are coordinated to the triamine portion and the pyridyldicarboxamide is unperturbed. Treatment of LH₂ with [MesCu]_<i>x</i> (Mes = mesityl) provided a monocopper­(I) complex, again with the metal coordinated only to the trialkylamine donor set. Reaction of [(LH₂)­CuCl]­OTf with NaOMe resulted in an unexpected migration of the copper­(II)–chloride fragment to the pyridyldicarboxamide site to yield Na­[LCuCl], from which a dicopper complex LCu₂Cl₂ and mixed-metal complexes LCu­(Cl)­M­(Cl) (M = Pd, Pt) were prepared by addition of CuCl₂ or MCl₂, respectively. The heterodinuclear complexes were also prepared by addition of CuCl₂ to [(LH₂)­MCl]­Cl

Photophysical Properties and Kinetic Studies of 2-Vinylpyridine-Based Cycloplatinated(II) Complexes Containing Various Phosphine Ligands

A series of cycloplatinated(II) complexes with general formula of [PtMe(Vpy)(PR3)], Vpy = 2-vinylpyridine and PR3 = PPh3 (1a); PPh2Me (1b); PPhMe2 (1c), were synthesized and characterized by means of spectroscopic methods. These cycloplatinated(II) complexes were luminescent at room temperature in the yellow–orange region’s structured bands. The PPhMe2 derivative was the strongest emissive among the complexes, and the complex with PPh3 was the weakest one. Similar to many luminescent cycloplatinated(II) complexes, the emission was mainly localized on the Vpy cyclometalated ligand as the main chromophoric moiety. The present cycloplatinated(II) complexes were oxidatively reacted with MeI to yield the corresponding cycloplatinated(IV) complexes. The kinetic studies of the reaction point out to an SN2 mechanism. The complex with PPhMe2 ligand exhibited the fastest oxidative addition reaction due to the most electron-rich Pt(II) center in its structure, whereas the PPh3 derivative showed the slowest one. Interestingly, for the PPhMe2 analog, the trans isomer was stable and could be isolated as both kinetic and thermodynamic product, while the other two underwent trans to cis isomerization