From Antiaromatic Norcorrolatonickel(II) to Aromatic and Nonaromatic Zwitterions: Innocent Ligands with Unbalanced Charge of the Core

A three-component reaction of antiaromatic meso-mesityl-3-nitronorcorrolatonickel(II) 1-NO2 with dialkyl acetylenedicarboxylate and PBu3 yields aromatic zwitterionic corrole nickel(II) complexes 3-R with one of the meso-substituents comprising a positively charged tributyl phosphonium group and negatively charged coordination core. Reaction of 1-NO2 with PBu3 alone resulted in a nonaromatic chiral adduct 5 of a zwitterionic phlorine character with a −PBu3+ group at a pyrrole β-position.

S2 | S I

Computational methods S4
Table S1 Crystal data for 3-Et S6 Table S2 Crystal data for 5 S7 Synthesis and characterization S8-S13 Figures S1-S8. NMR spectra of 3-Me S14-S20  Table S3. Electrochemical potentials for 3-R, 4-R, and 5 S85 Table S4. Computational details for structures discussed in the paper S85 References S86 S5 | S I parametrization) to meet standard convergence criteria, and the existence of a local minimum was verified by a normal mode frequency calculation. DFT calculations were performed by using the hybrid B3LYP functional [6][7][8] functional combined with the 6-31G(d,p) basis set for organic part of analyzed molecules and LANL2DZ pseudopotential for nickel(II) center. The structure optimization results are collected in the Table S3. The electronic spectra were simulated by means of time-dependent density functional theory (TD-DFT) using the Tamm-Dancoff approximation for 50 states. The electronic transitions and UV/Vis/NIR as well as CD spectra were analyzed by means of the GaussSum program. [9] The transitions were convoluted by Gaussian curves with 2000 cm -1 half line width. The population analysis was performed with NBO5.0 package implemented in Gaussian. The charge distribution was analyzed with Multiwfn 3.7. The graphic representation was obtained with an application of Multiwfn package and GaussView5.0 with using a formatted check point files.

General procedure for addition of dialkyl acetylenedicarboxylate and tributyl phosphine to 3-nitrocorrolatonickel(II) 1-NO 2
A solution of NO 2 -norcorrole nickel complex 1-NO 2 (31 mg, 0.05 mmol), Bu3P (62 mg, 0.25 mmol) and dimethyl acetylenedicarboxylate (62 mg, 0.5 mmol) or diethyl acetylenedicarboxylate (80 mg, 0.5 mmol) in 4 mL of dichloromethane was stirred at room temperature for 2 h. The solvent was then evaporated under vacuum. The residue was chromatographed on a silica gel column with dichloromethane as eluent. Green product fraction was collected. After solvent removal, the solid was washed with hexane to afford the desired product as a brown powder for 3-Me in 52% yield (24 mg) and 3-Et in 51% yield (25 mg).
Selected data for 3-Me and 3-Et:

Hydrolysis of 3-R
A sample of 20 mg of 3-Me or 3-Et was dissolved in 2 mL of chloroform/ethanol mixture (80/20 v/v) and 50 mg of basic alumina (Brockman 3⁰) was added. The slurry was sonicated in ultrasonic bath for 1-3 h. The solid was then separated from the solution by filtration and washed with 2 portion of 5 mL of chloroform. The filtrate was then evaporated to dryness, dissolved in dichloromethane and passed a short silica-gel column. The red eluate was collected and evaporated to 10% of its original volume. The product 4 was precipitated by addition of hexane

Addition of tributyl phosphine to 3-nitrocorrolatonickel(II) 1-NO 2
A sample of 12 mg (0.02 mmol) of 1-NO 2 was dissolved in 1 mL of chloroform and 10 L of tributylphosphine (8 mg, 0.04 mmol) was added. The sample turned blue after 5 minutes. The reaction mixture was allowed to react for 2 h at room temperature until TLC analysis indicated disappearance of the starting material. The sample was then passed down a short silica column with dichloromethane as eluent and the purple fraction was collected. The product was precipitated by addition of hexane and collected by filtration. Yield: 7.5 mg (47%). The crystals suitable for X-ray diffraction analysis were obtained by a slow diffusion od hexane into dichloroethane solution of 5.      [M] +                        Figure S65. 1