The homoleptic sandwich compounds - Mo and W biscorroles - have afforded a novel platform for experimental studies of relativistic effects. A 200 mV difference in reduction potential and a remarkable 130 nm shift of a near-IR spectral feature have been identified as manifestations of relativistic effects on the properties of these complexes.

A combination of quantum chemical calculations and synthetic studies was used to address the possibility of very high (>6) valence states of transition metals in porphyrin-type complexes. With corrole as a supporting ligand, DFT calculations ruled out Re(VII) and Ir(VII) dioxo complexes as stable species. Attempted rhenium insertion into benzocarbaporphyrin (BCP) ligands on the other hand led to two products with different stoichiometries - Re[BCP]O and Re[BCP]O₂. To our surprise, single-crystal structure determination of one of the complexes of the latter type indicated an Re^VO center with a second oxygen bridging the Re-C bond. In other words, although the monooxo complexes Re[BCP]O are oxophilic, the BCP ligand cannot sustain a trans-Re^VII(O)₂ center. The search for metal valence states >6 in porphyrin-type ligand environments must therefore continue.

Single-crystal X-ray analysis of the β-heptakis(trifluoromethyl)-meso-tetrakis(p-fluorophenyl)porphyrin, H₂ [(CF₃ )₇ TpFPP], has revealed the first example of a stable cis tautomer of a free-base porphyrin, the long-postulated intermediate of porphyrin tautomerism. The stability of the unique molecule appears to reflect a dual origin: a strongly saddled porphyrin skeleton, which alleviates electrostatic repulsion between the two NH protons, and two polarization-enhanced, transannular N-H⋅⋅⋅O-H⋅⋅⋅N hydrogen bond chains, each involving a molecule of water. DFT calculations suggest that the observed tautomer has a lower energy than the alternative, doubly hydrated trans tautomer by some 8.3 kcal mol^-1 . A fascinating prospect thus exists that H₂ [(CF₃ )₇ TpFPP]⋅2 H₂ O and cognate structures may act as supramolecular synthons, which, given their chirality, may even be amenable to resolution into optically pure enantiomers.

A series of metal-metal bonded osmium corrole dimers, {Os[T pXPC]}₂, were synthesized in reasonably good yields (35-46%) via the interaction of the corresponding free-base meso-tris( p-X-phenyl)corroles (H₃[T pXPC], X = CF₃, H, CH₃, and OCH₃), Os₃(CO)₁₂, and potassium carbonate in 1,2,4-trichlorobenzene under an inert atmosphere at 180 °C over several hours. The complexes are only the second class of Os corroles reported to date (the first being Os^VIN corroles) and also the second class of metal-metal bonded metallocorrole dimers (the other being Ru corrole dimers). Comparison of the X-ray structures, redox potentials, and optical spectra of analogous Ru and Os corrole dimers, along with scalar-relativistic DFT calculations, has provided an experimentally calibrated account of relativistic effects in these complexes. Three of the Os corrole dimers (X = CF₃, H, and OCH₃) were analyzed with single-crystal X-ray diffraction analysis, revealing inversion-related corrole rings with eclipsed Os-N bonds and Os-Os distances of ∼2.24 Å that are ∼0.06 Å longer than the Ru-Ru distances in the analogous Ru corrole dimers. Interestingly, a comparison of scalar-relativistic and nonrelativistic DFT calculations indicates that this difference in metal-metal bond distance does not, in fact, reflect a differential relativistic effect. For a given corrole ligand, the Ru and Os corrole dimers exhibit nearly identical oxidation potentials but dramatically different reduction potentials, with the Os values ∼0.5 V lower relative to Ru, suggesting that whereas oxidation occurs in a ligand-centered manner, reduction is substantially metal-centered, which indeed was confirmed by scalar-relativistic calculations. The calculations further indicate that approximately a third of the ∼0.5 V difference in reduction potentials can be ascribed to relativity. The somewhat muted value of this relativistic effect appears to be related to the finding that reduction of an Os corrole dimer is not exclusively metal-based but that a significant amount of spin density is delocalized over to the corrole ligand; in contrast, reduction of an Ru corrole dimer occurs exclusively on the Ru-Ru linkage. For isoelectronic complexes, the Ru and Os corrole dimers exhibit substantially different UV-vis spectra. A key difference is a strong near-UV feature of the Os series, which in energy terms is blue-shifted by ∼0.55 V relative to the analogous feature of the Ru series. TDDFT calculations suggest that this difference may be related to higher-energy Os(5d)-based LUMOs in the Os case relative to analogous MOs for Ru.

Halterman corroles have been synthesized for the first time from pyrrole and Halterman's aldehyde via Gryko's "water-methanol method". These were derivatized to the corresponding copper complexes and subsequently to the β-octabromo complexes. Electronic circular dichroism spectra were recorded for the enantiopure copper complexes, affording the first such measurements for the inherently chiral Cu corrole chromophore. Interestingly, for a given configuration of the Halterman substituents, X-ray crystallographic studies revealed both P and M conformations of the Cu-corrole core, proving that the substituents, even in conjunction with β-octabromination, are unable to lock the Cu-corrole core into a given chirality. The overall body of evidence strongly indicates a dynamic equilibrium between the P and M conformations. Such an interconversion, which presumably proceeds via saddling inversion, provides a rationale for our failure so far to resolve sterically hindered Cu corroles into their constituent enantiomers by means of chiral HPLC.