μ-Oxo-bis[(octacosafluoro-meso-tetraphenylporphyrinato)iron(iii)] – synthesis, crystal structure, and catalytic activity in oxidation reactions

Abstract

We describe the synthesis and X-ray crystal structure of µ-oxo-bis[(octacosafluoro-meso-tetraphenylporphyrinato)iron(III)] [(FeTPPF28)2O]. This novel iron complex is an efficient catalyst for oxidative biaryl coupling reactions of diarylamines and carbazoles. The asymmetric...

2,2′‐Bis(arylamino)‐1,1′‐biaryls as Building Blocks for the Synthesis of Dibenzo[d,f][1,3]diazepines, Dibenzo[d,f][1,3]diazepinones, and Dibenzo[c,e][1,2,7]thiadiazepine 6‐Oxides

“…[a] Reaction conditions: A: 3 (1.0 equiv), FePcF 16 (2×0.5 mol%), MsOH (10 mol%), CH 2 Cl 2 , rt, air; B: 3 (1.0 equiv), FePcF 16 (2×2.5 mol%), MsOH (50 mol%), CH 2 Cl 2 , rt, air; C: 3 (1.0 equiv), FePcF 16 (1×1.0 mol%), MsOH (10 mol%), CH 2 Cl 2 , rt, air (1×5.0 mol% FePcF 16 and 50 mol% MsOH for 3 e ); [34a] D: 3 (1.0 equiv), O(FeTPPF 28 ) 2 (1×1.5 mol%), BF 3 ⋅OEt 2 (20 mol%), CH 2 Cl 2 , rt, air; [34c] yields refer to isolated products. [b] Using reaction conditions B, cleavage of the acetal occurred.…”

“…It is important to note, that all of the iron‐catalyzed C−C coupling reactions using reaction conditions A and B were performed on gram scale using up to 2.5 g of starting material 3 . For the oxidative coupling of 3 a and 3 d , a recently reported procedure using μ ‐ oxo‐bis[(octacosafluoro‐ meso ‐tetraphenylporphyrinato)iron(III)] (O[FeTPPF 28 ] 2 ) (Figure 2) as catalyst in the presence of BF 3 ⋅OEt 2 as additive gave the best results, although only at extended reaction times (entries 1 and 4) [34c] . A high functional group tolerance was demonstrated by the presence of an acetal moiety in substrate 3 h which under the reaction conditions A (10 mol% MsOH) afforded the corresponding coupling product 4 h in 61 % yield (Table 1, entry 8).…”

Enhancing the performance for palladium catalysed tert-butyl hydroperoxide-mediated Wacker-type oxidation of alkenes

“…For example, in recent years, it has been shown that first-row transition metal catalysts can perform Wacker-type oxidation reactions, 7 with iron based systems showing particular promise. 8–13…”

“…For example, in recent years, it has been shown that first-row transition metal catalysts can perform Wacker-type oxidation reactions, 7 with iron based systems showing particular promise. [8][9][10][11][12][13] In the case of Pd based methods, an alternative approach to aerobic systems is to use peroxides to mediate these reactions. Peroxide-mediated Wacker reactions have been studied less than their aerobic counterparts, but some of the work to-date indicates they have the potential to address some of the limitations of aerobic systems.…”

Effect of para‐Substituents on meso‐Functionalized Oxidovanadium(IV) Porphyrins as Catalysts for Oxygen Atom Transfer Mediated Oxidation of Benzoin to Benzil under Mild Conditions

“…[21] Recently, the oxidation of deoxy benzoins to the corresponding 1,2-diones by Pd-nanoparticle catalyst and DMSO as an oxidant has been demonstrated. [22] Metalloporphyrins are very useful in chemical sensors, [23] nonlinear optics, [24] quantum information processing, [25] dyesensitized solar cells, [26,27] ultrafast dynamics, [28] therapeutics, [26,27] and catalysis; [29][30][31][32][33][34][35][36] some of them like Cr(IV), [37] Fe(III), [38,39] Co-(II) [40,41] and Mn(IV) [42] are very handy catalysts for OAT reactions because of their tailored spectral features and rich electrochemistry. [43][44][45] However, the catalytic oxidation of benzoin to benzil has never been explored using vanadium porphyrins.…”