Stable Inner 2H Tautomer of N-Confused-like Porphyrin Embedded with a Carbazole Subunit: Synthesis, Metal Coordination, and Magnetic and Anion Sensing Studies.

A new class of N-confused porphyrin 1 embedded with a carbazole subunit was prepared via [3 + 1] acid-catalyzed condensation of appropriate precursors. 1 underwent smooth metal complexation with Pd(II) and Cu(II) salts to provide the corresponding diamagnetic 1-Pd and paramagnetic 1-Cu, respectively. The single-crystal X-ray structure of 1-Pd is evident with a square-planar Pd-center through C-H activation of inverted pyrrole. Superconducting quantum interference device analysis combined with electron paramagnetic resonance (EPR) results provided insights into the paramagnetic nature of 1-Cu. Further, a ratiometric enhancement of near-IR fluorescence at 746 nm was found to be reversible upon adding CN- and F- ions. The solid-state structure of 1-Pd confirms that the anionic species is due to NH deprotonation.

From Sn(II) to Sn(IV): Enhancing Lewis Acidity Via Oxidation.

We demonstrate the increased Lewis acidity on going from Sn(II) to Sn(IV) by oxidizing TpMe2SnOTf (OTf = SO3CF3) to TpMe2SnF(OTf)2. Replacement of the fluoride ion in TpMe2SnF(OTf)2 by a triflate, resulting in TpMe2Sn(OTf)3 further enhances the Lewis acidity at tin. 119Sn NMR spectroscopy, modified Gutmann-Beckett test, computational analysis, and catalytic phosphine oxide deoxygenation support the claims.

Cationic Zinc Hydride Catalyzed Carbon Dioxide Reduction to Formate: Deciphering Elementary Reactions, Isolation of Intermediates, and Computational Investigations.

Zinc has been an element of choice for carbon dioxide reduction in recent years. Zinc compounds have been showcased as catalysts for carbon dioxide hydrosilylation and hydroboration. The extent of carbon dioxide reduction can depend on various factors, including electrophilicity at the zinc center and the denticity of the ancillary ligands. In a few cases, the addition of Lewis acids to zinc hydride catalysts markedly influences carbon dioxide reduction. These factors have been investigated by exploring elementary reactions of carbon dioxide hydrosilylation and hydroboration by using cationic zinc hydrides bearing tetradentate tris[2-(dimethylamino)ethyl]amine and tridentate N,N,N',N'',N''-pentamethyldiethylenetriamine in the presence of triphenylborane and tris(pentafluorophenyl)borane.

Consequence of Ligand Bite Angle on Bismuth Lewis Acidity.

Ligand bite angle, a common parameter to fine-tune reactivity in transition-metal chemistry, is used for the first time in main-group chemistry to control and tune the Lewis acidity in organobismuth cations bearing 2-[(dimethylamino)methyl]phenyl (Me2NCH2C6H4) and 2-(dimethylamino)phenyl (Me2NC6H4) ligands. The latter chelating ligand induces a shorter C-Bi-N bite angle, leading to a weaker Bi-N bond with a corresponding lower Bi-N σ*-acceptor orbital and hence exhibiting remarkably higher Lewis acidity. The Gutmann-Beckett method is successfully employed to quantify the Lewis acidity in organobismuth cations.

Carbazole-embedded p-benziporphyrinoid: synthesis, structure and a reversible chemodosimeter for mercury(II) ions.

The first carbazole-embedded p-benziporphyrinoid is synthesized by a [3+1] acid-catalyzed condensation between appropriate coupling partners. The macrocycle 1 exhibited orange emission and showed a large Stokes shift of 5831 cm-1. Intriguingly, it shows a selective affinity towards Hg2+ ions over other metal-ions in a reversible manner. Job's plot confirmed the 1 : 1 stoichiometry with unambiguous confirmation of both 1 and 1-Hg by single crystal X-ray analysis.

Reactivity of a quasi-four-coordinate butylmagnesium cation.

We present the reactivity of the Mg-C and the ß-CH bonds in the trigonal pyramidal [(pmdta)Mg(nBu)]+ exhibiting a weak Mg⋯F interaction with counter anion, [B(C6F5)4]-. Instantaneous ß-hydride reactivity with benzophenone, reductive alkylation of phenyl benzoate, and straightforward synthesis of [(pmdta)MgH]+via metathesis with pinacolborane/phenylsilane are discussed.

Amidomagnesium cations.

We report the synthesis, structure and reactivity of molecular amidomagnesium cations bearing tris{2-(dimethylamino)-ethyl}amine (Me6TREN). Me6TREN binds to the cationic magnesium centre exhibiting κ4 and κ3 coordination modes in [Me6TREN-Mg-N(SiHMe2)2]+ and [Me6TREN-Mg-N(SiMe3)2]+ respectively. [Me6TREN-Mg-N(SiHMe2)2]+ reacts with benzophenone resulting in the insertion of the carbonyl group across ß-SiH bond. The reaction between [Me6TREN-Mg-N(SiMe3)2]+ and CO2 leads to [Me6TREN-Mg-OSiMe3]+, while the reaction with H2O results in [Me6TREN-Mg-OH]22+. Attempts to prepare hydridomagnesium cations from [Me6TREN-Mg-N(SiMe3)2]+ using KH resulted in the precipitation of MgH2 and the isolation of [(Me6TREN)K(THF)3]+.

Terminal hydridozinc cation.

A thermally stable terminal hydridozinc cation has been isolated. The nucleophilicity of the hydride ligand is demonstrated by inserting carbon dioxide, carbodiimide and benzophenone across the Zn-H bond in a facile manner. Preliminary studies on catalytic hydrosilylation using PhSiH3 indicate that the hydridozinc cation in the presence of BPh3 can selectively reduce CO2 to PhSi(OCHO)3.

Organoaluminum cations for carbonyl activation.

In search of stable, yet reactive aluminum Lewis acids, we have isolated an organoaluminum cation, [(Me2NC6H4)2Al(C4H8O)2]+, coordinated with two labile tetrahydrofuran ligands. Its catalytic performance in aldehyde dimerization reveals turn-over frequencies reaching up to 6000 h-1, exceeding that of the reported main group catalysts. The cation is further demonstrated to catalyze hydroelementation of ketones. Mechanistic investigations reveal that aldehyde dimerization and ketone hydrosilylation occur through carbonyl activation.

Manifestation of helicity in one-dimensional iodobismuthate.

We report here, the first example of an inorganic-organic hybrid material incorporating a helical iodobismuthate [BiI4]∞ templated by 2,6-diisopropylanilinium cations. The realisation of the helical iodobismuthate opens up the possibility of a wide range of physical properties among hybrid materials.