Journal of Molecular Catalysis A: Chemical 251 (2006) 263–269 Synthesis, spectroscopy, and structures of chiral rhodium(I) corrole complexes Irena Saltsman a , Yael Balazs a , Israel Goldberg b,∗∗ , Zeev Gross a,∗ a Department of Chemistry and Institute of Catalysis Science and Technology, Technion-Israel Institute of Technology, Haifa 32000, Israel b School of Chemistry, Tel Aviv University, Tel Aviv 69978, Israel Available online 20 March 2006 Abstract The easily accessible chiral corrole 1 was metallated by rhodium and isolated with additional ligands of very different electronic and steric properties: two carbonyls, a cyclic diphosphine, and a diene. The diamagnetic rhodium(I) complexes were characterized by multinuclear NMR methods and X-ray crystallography. The diphosphine-coordinated complex 2b was obtained non-racemic, which was further confirmed by circular dichroism. © 2006 Elsevier B.V. All rights reserved. Keywords: Rhodium complexes; Corroles; X-ray crystallography 1. Introduction The recently introduced synthetic methodologies for facile preparation of triarylcorroles [1], coordination-core contracted analogs of tetraarylporphyrins, allowed for the utilization of the corresponding metal complexes as catalysts for various trans- formations [2,3]. These include hydroxylation of alkanes [2] and epoxidation [4], aziridination [5], and cyclopropanation [6] of alkenes. Triphenylphosphine-coordinated rhodium(III) cor- roles were shown to be potent catalysts for carbene-transfer from ethyl diazoacetate (EDA) to olefins [6] and several such complexes were fully characterized by NMR and X-ray crys- tallography [6,7]. The present investigations focuson the recently introduced chiral corrole 1 (Scheme 1) [8] as the firststep toward catalysis by chiral corrole metal complexes. We report the syntheses of several rhodium(I) complexes of 1 thatdiffer significantly in the steric and electronic features of the othermetal-coordinated ligands. All complexes were fully characterized by multinuclear NMR methods and X-ray crystallography. ∗ Corresponding author. Fax: +972 4 829 5703. ∗∗ Corresponding author. Fax: +972 3 640 9293. E-mail addresses: goldberg@chemsg7.tau.ac.il (I. Goldberg), chr10zg@tx.technion.ac.il (Z. Gross). 2. Experimental 2.1.Physical methods NMR spectra were recorded at room temperature on a BrukerAvance300 spectrometer (AV300)equipped with a QNP 1H/19F/31P/13C-2H 5 mm probehead (operating at 300 MHzfor 1 H and 282 MHzfor 19 F) or on a Bruker Avance 500 spectrometer (AV500) equipped with a bbo probe- head (operating at 500 MHz for 1 H, 202 MHz for 31 P, and 125 MHz for 13 C). Chemical shifts are reported in ppm rela- tive to solvent signals (δ H = 7.15 and δ C = 128.0 for benzene- d 6 or δ H = 7.24 and δ C = 77.0 for chloroform-d) or relative to CFCl 3 (δ F = 0.00). Coupling constants (J) are reported in Hz. The 19 F-decoupled 1 H-observed NMR spectra were recorded on the AV300 using the zghfigqn pulse program (XWIN-NMR Version 3.1) and waltz16 composite pulse decoupling. Con- trol experiments were run with full attenuation (120 dB) on the 19 F pulses, but otherwise identical conditions. 31 P-decoupling of 1 H-observed NMR spectra was achieved with cw irradia- tion on the AV500 using the zgcw pulprogram (45 dB atten- uation ofthe X-amplifier or 120 dB attenuation in control experiments). 13 C NMR spectra were acquired with inverse-gated 1 H decoupling on the AV500; a totalof 20,480 transients were 1381-1169/$ – see front matter © 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.molcata.2006.02.030