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 series of stable Pt(IV) corrole complexes with the general formula Pt^IV[TpXPC](m/p-C₆H₄CN)(py), where TpXPC^3- is the trianion of a tris(p-X-phenyl)corrole and X = CF₃, H, and CH₃, has been synthesized, affording key physicochemical data on a rare and elusive class of metallocorroles. Single-crystal X-ray structures of two of the complexes revealed very short equatorial Pt-N distances of 1.94-1.97 Å, an axial Pt-C distance of ∼2.03 Å, and an axial Pt-N distance of ∼2.22 Å. The complexes exhibit Soret maxima at ∼430 nm, which are essentially independent of the meso-aryl para substituents, and strong Q bands with the most intense peak at 595-599 nm. The substituent-independent Soret maxima are consistent with an innocent Pt^IV-corrole^3- description for the complexes. The low reduction potentials (-1.45 ± 0.08 V vs saturated calomel reference electrode) also support a highly stable Pt(IV) ground state as opposed to a noninnocent corrole^•2- description. The reductions, however, are irreversible, which suggests that they involve concomitant cleavage of the Pt-aryl bond. Unlike Pt(IV) porphyrins, two of the complexes, Pt^IV[TpXPC](m-C₆H₄CN)(py) (X = CF₃ and CH₃), were found to exhibit room-temperature near-IR phosphorescence with emission maxima at 813 and 826 nm, respectively. The quantum yield of ∼0.3% is comparable to those observed for six-coordinate Ir(III) corroles.

As part of our efforts to develop rhenium-oxo corroles as photosensitizers for oxygen sensing and photodynamic therapy, we investigated the potential β-perhalogenation of five ReO meso-tris(para-X-phenyl)corroles, Re[TpXPC](O) (X = CF₃, H, F, CH₃, and OCH₃), with elemental chlorine and bromine. With Cl₂, β-octachlorinated products Re[Cl₈TpXPC](O) were rapidly obtained for X = CF₃, H, and CH₃, but X = OCH₃ resulted in overchlorination on the meso-aryl groups. Full β-octabromination proved slower relative to Cu and Ir corroles, but the desired Re[Br₈TpXPC](O) products were finally obtained for X = H and F after a week at room temperature. For X = CH₃ and OCH₃, these conditions led to undecabrominated products Re[Br₁₁TpXPC](O). Compared to the β-unsubstituted starting materials, the β-octahalogenated products were found to exhibit sharp ¹H NMR signals at room temperature, indicating that the aryl groups are locked in place by the β-halogens, and substantially redshifted Soret and Q bands. Single-crystal X-ray structures of Re[Cl₈TpCF₃PC](O), Re[Cl₈TpCH₃PC](O), and Re[Br₈TpFPC](O) revealed mild saddling for one Cl₈ structure and the Br₈ structure. These structural variations, however, appear too insignificant to explain the slowness of the β-octabromination protocols, which seems best attributed to the deactivating influence of the high-valent Re center.

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.

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.

Metallocorroles involving 5d transition metals are currently of interest as near-IR phosphors and as photosensitizers for oxygen sensing and photodynamic therapy. Their syntheses, however, are often bedeviled by capricious and low-yielding protocols. Against this backdrop, we describe rhenium-imido corroles, a new class of 5d metallocorroles, synthesized simply and in respectable (∼30%) yields via the interaction of a free-base corrole, Re₂(CO)₁₀, K₂CO₃, and aniline in 1,2,4-trichlorobenzene at ∼190 °C in a sealed vial under strict anaerobic conditions. The generality of the method was shown by the synthesis of six derivatives, including those derived from meso-tris(pentafluorophenyl)corrole, H₃[TPFPC], and five different meso-tris(p-X-phenyl)corroles, H₃[TpXPC], where X = CF₃, F, H, CH₃, OCH₃. Single-crystal X-ray structures obtained for two of the complexes, Re[TpFPC](NPh) and Re[TpCF₃PC](NPh), revealed relatively unstrained equatorial Re-N distances of ∼2.00 Å, a ∼ 0.7-Å displacement of the Re from the mean plane of the corrole nitrogens, and an Re-N_imido distance of ∼1.72 Å. Details of the corrole skeletal bond distances, diamagnetic ¹H NMR spectra, relatively substituent-independent Soret maxima, and electrochemical HOMO-LUMO gaps of ∼2.2 V all indicated an innocent corrole macrocycle. Surprisingly, unlike several other classes of 5d metallocorroles, the Re-imido complexes proved nonemissive in solution at room temperature and also failed to sensitize singlet oxygen formation, indicating rapid radiationless deactivation of the triplet state, presumably via the rapidly rotating axial phenyl group. By analogy with other metal-oxo and -imido corroles, we remain hopeful that the Re-imido group will prove amenable to further elaboration and thereby contribute to the development of a somewhat challenging area of coordination chemistry.

Vilsmeier-Haack formylation of ReO and Au meso-triarylcorroles over 16-18 hours affords moderate to good yields (47-65%) of the ReO-3-formyl and Au-3,17-diformyl derivatives in a highly regioselective manner. Formylation was found to effect substantial upshifts for redox potentials (especially the reduction potentials) as well as significant to dramatic redshifts for both the Soret and Q bands.