A facile inner halogenation of Ag(III) NCP complex1is reported. Treatment of1with 2NHCl and 1NHBr gave2and4, respectively. A demetallized product3was formed as a trace side product when dilute acids were applied and as a predominant product when treated with concentrated acids. The importance of the C3‐ethoxy group for the halogenation reactions was experimentally indicated. Treatment of1with 4NH2SO4gave carbaporpholactam6in good yield. Halide anions are suggested to accelerate the demetallation reaction of1.

We report the synthesis, characterization, and reactivities of two stable Ni III N-confused porphyrin (NCP) complexes. Metalation of 3-OEt NCP 1 with NiCl 2 • 6H 2 O in CHCl 3 /EtOH gave 3-OEt Ni II NCP 3 initially, which was easily oxidized in air to form the Ni III complex of NCP inner Coxide 4. Bis-ethoxy-modified Ni III complex 5 was synthesized by oxidation of 3 with PIFA in ethanol and CHCl 3 . The structures of 4 and 5 were determined by single-crystal Xray diffraction analysis. An unusually long Ni III À C bond (2.170(9) Å) was observed in 4. The g-factor (g > 2.1) observed in the EPR spectra of 4 and 5 further confirmed that they are paramagnetic Ni III complexes. Comparative experiments showed that the 3-ethoxy group plays an important role in the formation of 4 and 5. Reduction of 4 and 5 with NaBH 4 regenerated complex 3. Organonickel(III) species have been regarded as key intermediates in many nickel-catalyzed reactions. [1] Therefore, it is of great significance to isolate organic Ni III complexes and examine their structures and properties for better understanding the roles of organic Ni III species and further developments of the Nicatalyzed reactions. [2] So far, several stable organonickel(III) complexes have been reported. For example, the Mirica group reported that the tetradentate ligand N,N '-di-tert-butyl-2,11diaza[3.3](2,6)-pyridinophane ( tBu N4) and its C-donor derivative tBu N3C À could be used to prepare Ni III complexes [3] (Figure 1a). The Sanford group reported that a facial tridentate tris (pyrazolyl)borate ligand supports a variety of isolable Ni III complexes [4] (Figure 1b). Diao group reported the synthesis of binuclear Ni III À Ni III complex [5] (Figure 1c). Despite these achievements, there is still a lot of room for the studies on the synthesis and reactivity of stable organonickel(III) compounds.N-Confused porphyrins (NCPs), [6] also called N-inverted porphyrins, are isomers of the regular porphyrins. Inversion of one pyrrole unit gives NCPs a unique skeleton consisting of an inner NNNC core and a nitrogen atom at the periphery. As ligands, NCPs were found to be able to form carbon-metal bonds and stabilize high oxidation states of many metals such as Mn III , Co III , Cu III , Ag III , Sb V and Re V . [7] Ni II NCPs was synthesized in 1994 by Latos-Grażyński group. [6b] Later, the same group reported in situ generation of the Ni III NCP species through oneelectron oxidation and subsequent metathesis of Ni II NCPs. [8] These Ni III NCP derivatives were characterized by EPR and 2 H NMR but were not isolated and structurally well characterized.

Rigid cyclic molecules are of great interest due to their intriguing structures and unique properties. Here, we report the facile synthesis of gem-linked cyclic tetraphenylethylenes and cyclic hexaphenylethylenes, namely [n]CTPEs...

Tubular structures offer a wide variety of applications, so designing such materials with distinct dimensions is highly desirable yet challenging. In the current report, we have demonstrated the synthesis of...

Conjugate addition of ethanol and subsequent oxidation with [Bis (trifluoroacetoxy)iodo]benzene (PIFA) were used to inner ethoxylation of 3‐oxo‐N‐confused tetraphenylporphyrin (ONCP). First oxidation of ONCP with PIFA followed by treatment with ethanol gave N‐confused phlorins 5 and 6.