Two-component relativistic time-dependent density functional theory calculations with spin-orbit coupling predict yellow and orange–red absorption for BiPh5 and BiMe5, respectively, providing an excellent explanation for their respective violet and blue–violet colors. According to the calculations, the visible absorption is clearly attributable to a single transition from a ligand-based HOMO ...

Given the many applications of ruthenium porphyrins, the rarity of ruthenium corroles and the underdeveloped state of their chemistry are clearly indicative of an area ripe for significant breakthroughs. The tendency of ruthenium corroles to form unreactive metal–metal-bonded dimers has been recognized as a key impediment in this area. Herein, by exposing free-base meso-tris(p-X-phenyl)corroles, ...

Presented herein is a first major density functional theory (BP86/D3/STO-TZ2P) survey of the energetics of saddling versus ruffling for a wide range of dodecasubstituted metalloporphyrins with M = Ni, Cu, Zn, Pd, and Pt. For the majority of X₈TPP (i.e., β-octasubstituted-meso-tetraphenylporphyrin), the calculations indicated a clear preference for the saddled conformation, consistent with ...

Copper undecaarylcorroles were found to undergo acid-induced demetalation with unusual ease under both reductive and nonreductive conditions. The resulting free-base undecaarylcorroles were found to be rather reactive, readily photooxygenating to yield 5/10-hydroxyisocorroles and open-chain tetrapyrroles. The use of nonreductive conditions led to 50-75% yields of undecaarylisocorroles, a new class ...

The first FeNO octabromocorroles have been synthesized including four β-octabromo-meso-tris(p-X-phenyl)corrole derivatives Fe[Br8TpXPC](NO) (X = CF3, H, CH3, OCH3) and the β-octabromo-meso-tris(pentafluorophenyl)corrole complex, Fe[Br8TPFPC](NO). The last complex, which proved amenable to single-crystal X-ray structure determination, exhibits the geometry parameters: Fe–N(O) 1.643(8) Å, N–O 1.158(9) ...

A one-pot protocol, effecting 14-fold bromination with elemental bromine, has afforded copper beta-octabromo-meso-tris(2,6-dibromo-3,5-dimethoxyphenyl)corrole, a new bis-pocket metallocorrole. The Cu complex underwent smooth demetalation under reductive conditions, affording the free corrole ligand, which in turn could be readily complexed to Mn^III and Au^III.A single-crystal ...

The difference in [3 + 2] cycloaddition reactivity between fac- [MO₃(tacn)]⁺ (M = Re, ⁹⁹Tc; tacn = 1,4,7-triazacyclononane) complexes has been reexamined with a selection of unsaturated substrates including sodium 4- vinylbenzenesulfonate, norbornene, 2-butyne, and 2-methyl-3-butyn-2-ol (2MByOH). None of the substrates was found to react with the Re cation in water ...

Relativistic and nonrelativistic density functional theory calculations were used to investigate rare or nonexistent ruthenium and osmium analogues of nitrosylhemes. Strong ligand field effects and, to a lesser degree, relativistic effects were found to destabilize {RuNO}⁷ porphyrins relative to their {FeNO}⁷ analogues. Substantially stronger relativistic effects account for ...

Platinum has been inserted into corroles for the first time and three oxidized PtIV(corrole2)ArAr0 complexes have been structurally characterized. The Soret maxima of these complexes exhibit an unusually strong dependence on the meso-aryl substituents on the corrole, indicating aryl - corrole2 charge transfer character in these transitions.

Dedicated to the memory of Björn Roos (1937–2010), one of the fathers of modern multiconfigurational quantum chemistry, who also cared deeply about chemical applications, and a fun and inspiring friend to countless theoretically oriented chemists.