Synthesis and Reactivity Studies of a Tin(II) Corrole Complex

Abstract

A series of tris(pentafluorophenyl)corrole (TPFC) tin(IV) and tin(II) complexes were prepared and studied by various characterization techniques including (1)H, (19)F, and (119)Sn NMR and UV-vis spectroscopy, mass spectrometry, and single-crystal X-ray diffraction. The unusual 4-coordinate, monomeric, divalent tin(II) complex [(TPFC)Sn(II)](-) (2a) showed highly efficient reactivity toward alkenes and alkyl halides via a nucleophilic addition pathway leading to the quantitative formation of alkyl stannyl corrole compounds. DFT calculations confirmed the divalent nature of the tin center in 2a, and an NBO analysis showed about 99.99% Sn lone pair character, of which 83.6% was Sn 5s and 16.35% was Sn 5p character.

Thermodynamic and reactivity studies of a tin corrole–cobalt porphyrin heterobimetallic complex

“…The Sn–Co bond was approximately perpendicular to both the corrole and the porphyrin planes, and the two ligand planes were aligned face-to-face. The Sn atom protruded noticeably (0.872 Å) from the N 4 -plane of the corrole ligand, comparable with known (TPFC)Sn–X complexes (0.776–0.798 Å), 11 while the Co atom was essentially within the porphyrin plane (the distance to the N1–N2–N3–N4 mean plane was 0.102 Å).…”

“…S5a † ). The chemical shifts of the latter species (8.88, 8.34, 8.14, and 7.82 ppm) resembled those of (TPFC)Sn–CH 2 –Sn(TPFC), 11 suggesting that the species was the μ-oxo dimer (TPFC)Sn–O–Sn(TPFC) ( 6 ). This assignment was confirmed by the independent synthesis of 6 from aerobic oxidation of 4 (see the ESI † ) and the single crystal XRD structure ( Fig.…”

“…Previously, we reported the synthesis of corrole Ge( iii ) radicals, 9 Ge( iv ) cation complexes, 10 and a corrole Sn( ii ) complex. 11 However, the preparation of high valent corrole tin complexes with well-exposed tin centers, i.e. corrole Sn( iii ) radicals and Sn( iv ) cations, is impeded by the inert pair effect, i.e.…”

Oxo(corrolato)vanadium(iv) catalyzed epoxidation: oxo(peroxo)(corrolato)vanadium(v) is the true catalytic species

“…[30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49] Corrole has excellent chelating properties; many metal complexes across the periodic table bearing corrole ligand functionalities have already been reported in the literature. [50][51][52][53][54][55][56][57][58][59][60][61][62][63] Licoccia et al first synthesized oxo(corrolato)vanadium(IV) complexes bearing b-substitution at the corrole periphery. 64 Interestingly, to date, there is no report on the oxo(corrolato)vanadium(IV) complexes bearing meso-substitution at the corrole periphery.…”

Fighting Cancer with Corroles

“…44–45 One important consequence of enhanced covalency is that metallocorroles are stable toward hydrolysis, 46 and not prone to metal ion loss under physiologically relevant conditions. 47 The combination of σ metal-ligand covalency and π-electron noninnocence means that metal oxidation states are hard to assign in many cases. It follows that the oxidation states adopted in this review must be viewed as “formal” ones in which the chelating corrole is assumed to be a trianionic closed-shell ligand.…”