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Electronic Structure of Manganese Corroles Revisited: X-ray Structures, Optical and X-ray Absorption Spectroscopies, and Electrochemistry as Probes of Ligand Noninnocence

Journal Article · · Inorganic Chemistry
 [1];  [2];  [3];  [2];  [4];  [1]
  1. UiT- The Artic Univ. of Norway, Tromso (Norway)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Univ. of the Free State, Bloemfontein (Republic of South Africa)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
+ Show Author Affiliations

Presented herein is a detailed multitechnique investigation of ligand noninnocence in S = 3/2 manganese corrole derivatives at the formal MnIV oxidation state. The Soret maxima of Mn[TpXPC]Cl (TpXPC = meso-tris(p-X-phenyl)corrole, where X = CF3, H, Me, and OMe) were found to red-shift over a range of 37 nm with increasing electron-donating character of X. For Mn[TpXPC]Ph, in contrast, the complex Soret envelopes were found to be largely independent of X. These observations suggested a noninnocent corrole•2–-like ligand for the MnCl complexes and an innocent corrole3– ligand for the MnPh complexes. Single-crystal X-ray structures of three Mn[TpXPC]Cl complexes revealed skeletal bond-length alternations indicative of a noninnocent corrole, while no such alternation was observed for Mn[TpOMePC]Ph. B3LYP density functional theory (DFT) calculations on Mn[TPC]Cl yielded strong spatial separation of the α and β spin densities, consistent with an antiferromagnetically coupled MnIII-corrole•2– description. By comparison, relatively little spatial separation of the α and β spin densities was found for Mn[TPC]Ph, consistent with an essentially MnIV-corrole3– description. X-ray absorption of near-edge spectroscopy (XANES) revealed a moderate blue shift of 0.6 eV for the Mn K-pre-edge of Mn[TpCF3PC]Ph and a striking enhancement of the pre-edge intensity, relative to Mn[TpCF3PC]Cl, consistent with a more oxidized, i.e., MnIV, center in Mn[TpCF3PC]Ph. Time-dependent DFT calculations indicated that the enhanced intensity of the Mn K-pre-edge of Mn[TpCF3PC]Ph results from the extra 3dz2 hole, which mixes strongly with the Mn 4pz orbital. Combined with similar results on Fe[TPC]Cl and Fe[TPC]Ph, the present study underscores the considerable potential of metal K-edge XANES in probing ligand noninnocence in first-row transition-metal corroles. As a result, cyclic voltammetry measurements revealed highly negative first reduction potentials for the Mn[TpXPC]Ph series (~–0.95 V) as well as large electrochemical HOMO-LUMO gaps of ~1.7 V. The first reductions, however, are irreversible, suggesting cleavage of the Mn–Ph bond.

Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1457057
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 24 Vol. 56; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (2)

Stable Platinum(IV) Corroles: Synthesis, Molecular Structure, and Room-Temperature Near-IR Phosphorescence journal August 2018
Bis‐copper(II) Complex of Triply‐linked Corrole Dimer and Its Dication journal August 2018

Figures / Tables (18)

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Table 1(p. 6)table Table 1
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Table 2(p. 9)table Table 2
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