Synthesis, structures and alkane oxygenation reactivity of bioinspired fluoroalkyl iron phthalocyanines

Author:

Zhort Mufeda1,Lee Hyun-Jin2,Gorun Sergiu M.1

Affiliation:

1. Department of Chemistry and Biochemistry and Center for Functional Materials, Seton Hall University, South Orange, New Jersey 07079, USA

2. Department of Chemistry, Brown University, Providence, Rhode Island 02912, USA

Abstract

We report the synthesis, structural characterization and reactivity of perfluoroalkyl (R[Formula: see text] substituted perfluoro phthalocyanines, [F[Formula: see text]PcFe(II)L2], L = axial H2O, methanol or pyridine, and [F[Formula: see text]PcFe(III)L], L = methoxy and cyanide anions. X-ray structures of the Fe(II) complexes reveal that axial H2O and methanol are nested in the hydrophobic R[Formula: see text] pocket of the macrocycle. The aqua complexes exhibit columnar stacking with a central linear chain of H-bonded H2O-Fe-H2O groups that form a hydrophilic, linear “core“embedded in surrounding R[Formula: see text] groups. The electron-deficient fluoroalkyl fluoro ([Formula: see text]-C3F[Formula: see text]F8PcFe(II)L2 complexes are all low-spin, diamagnetic, unlike the F[Formula: see text]PcFe complex, L = H2O, which is paramagnetic. The P450-related PcFe(II) complexes, which exhibit no macrocyclic C-H bonds, catalyze cyclohexane (C[Formula: see text] oxygenations using both t-butyl hydroperoxide (TBHP) and air, without noticeable catalyst decomposition, to produce C6-alcohol and C6-ketone in ~1:1 ratio (KA-oil). Relatively high TOFs, 180 and 85/hr, are observed for TBHP and O2-based oxygenations, respectively. No catalyst decomposition is observed for at least 8 hours, even up to 100[Formula: see text]C, when O2 is the oxidant, in the absence of a co-reductant. Fluoroalkylated phthalocyanine iron catalysts lacking C-H bonds could be suitable for other aerobic oxidations and oxygenations.

Publisher

World Scientific Pub Co Pte Ltd

Subject

General Chemistry

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