Hydrogen-Bonded Dioxygen Adduct of an Iron Porphyrin with an Alkanethiolate Ligand: An Elaborate Model of Cytochrome P450

Abstract

A stable dioxygen adduct is formed from a synthetic analogue for cytochrome P450, which has an alkanethiolate ligand and hydroxyl groups inside the molecular cavities (see scheme). The structure exhibits the first clear evidence for a hydrogen bond to bound dioxygen among thiolate‐coordinated hemes, including the enzymes.

New approach to the activation of anti-cancer pro-drugs by metalloporphyrin-based cytochrome P450 mimics in all-aqueous biologically relevant system

“…Synthetically prepared metalloporphyrins, highly stable low-molecular weight molecules capable of catalyzing electron-transfer reactions, have been successfully utilized in industrial catalysis, as imaging contrast agents, in photodynamic therapy [10,11] and as biological catalysts -enzyme mimics [12][13][14][15][16][17][18][19][20]. Both the Fe and Mn porphyrins have been studied as mimics of cytochrome P450 in oxidation, epoxidation, and hydroxylation in the presence of oxidants [21][22][23][24][25][26][27][28][29][30][31] and reductants/excess oxygen either in organic or biphasic systems [32][33][34][35][36][37][38].…”

Vibrational analysis of Ni(II) complex with 4,12-ditolyl-16,24-diphenyl-3-thiaporphyrin (SDTDPPNi(II)Cl) and its isotopic labeled (61Ni(II), −d6, and −d10) derivatives

“…1619 ν(C 63 -C 64 ) [11]+ν(C 60 -C 61 ) [11]+ν(C 47 -C 48 ) [11]+ν(C 50 -C 46 ) [11] 49-27 32 0 0 1619 ν(C 63 -C 64 ) [11], ν(C 60 -C 61 ) [11], ν(C 47 -C 48 ) [11], ν(C 50 -C 46 ) [11] 32 0 0 1616 ν(C 73 -C 71 ) [11], ν(C 70 -C 72 ) [11], ν(C 41 -C 42 ) [11], ν(C 40 -C 44 ) [11] 0 0 0 1616 ν(C 73 -C 71 ) [11], ν(C 70 -C 72 ) [11], ν(C 41 -C 42 ) [11], ν(C 40 -C 44 ) [11] 0 0 0 1597 1601 1592 ν(C 62 -C 63 ) [9], ν(C 61 -C 62 ) [9], ν(C 49 -C 50 ) [9], ν(C 48 -C 49 ) [9] 49-27 39 0 0 1591 ν(C 62 -C 63 ) [10], ν(C 61 -C 62 ) [10], ν(C 49 -C 50 ) [10], ν(C 48 -C 49 ) [10] 35 0 0 1590 ν(C 74 -C 73 ) [10], ν(C 72 -C 74 ) [10], ν(C 44 -C 43 ) [10], ν(C 42 -C 43 ) [10] 0 0 0 1589 ν(C 74 -C 73 ) [10], ν(C 72 -C 74 ) [10], ν(C 44 -C 43 ) [10], ν(C 42 -C 43 ) [10] -1 0 0 1573 1560 1567 ν(C 24 -C 35 ) [11], ν(C 18 -C 24 ) [14], ν(C 16 -C 25 ) [10], ν(C 19 -C 16 ) [20] -3 11-53 3 0 [5], δ(H 76 -C 73 -C 74 ) [7], δ(H 78 -C 72 -C 70 ) [6],…”

“…, ν(C 46 -C 34 ) [7], ν(C 64 -C 17 ) [7], ν(C 60 -C 17 ) [7], δ(H 51 -C 46 -C 34 ) [5], δ(H 65 -C 64 -C 17 ) [ [11], δ(H 59 -C 49 -C 48 ) [18], δ(H 58 -C 48 -C 47 ) [10], δ(H 66 -C 63 -C 64 ) [11], δ(H 67 -C 62 -C 61 ) [18], δ(H 68 -C 61 -C 60 ) [10] 337-338 332 0 0 1183 δ(H 52 -C 50 -C 46 ) [11], δ(H 59 -C 49 -C 48 ) [19], δ(H 58 -C 48 -C 47 ) [10], δ(H 66 -C 63 -C 64 ) [11], δ(H 67 -C 62 -C 61 ) [19], δ(H 68 -C 61 -C 60 ) [10] 332 0 0 1155 1163 ν(C 10 -C 8 ) [8], ν(C 10 -C 7 ) [9], ν(C 8 -C 6 ) [8], δ(H 9 -C 8 -C 6 ) [5], δ(H 11 -C 10 -C 7 ) [ [9], ν(C 70 -C 72 ) [8], ν(C 41 -C 42 ) [8], ν(C 40 -C 44 ) [9], δ(H 77 -C 74 -C 72 ) [7], [9], ν(C 60 -C 61 ) [9], ν(C 47 -C 48 ) [9], ν(C 50 -C 46 ) [9], δ(H 59 -C 49 -C 48 ) [7], δ(H 67 -C 62 -C 61 ) [7] 242-248 133 1 0…”

“…1086 ν(C 63 -C 64 ) [10], ν(C 60 -C 61 ) [10], ν(C 47 -C 48 ) [10], ν(C 50 -C 46 ) [10] 134 1 0 1072 1076 ν(C 10 -C 8 ) [15], δ(H 9 -C 8 -C 6 ) [15], δ(H 11 -C 10 -C 7 ) [15] 1 -30 0 1035 1044 ν(C 62 -C 63 ) [8], ν(C 61 -C 62 ) [7], ν(C 49 -C 50 ) [8], ν(C 48 -C 49 ) [7], ν(C 47 -C 34 ) [5], ν(C 46 -C 34 ) [5], ν(C 64 -C 17 ) [5], ν(C 60 -C 17 ) [5] 91 9 0…”

“…Iron complexes of porphyrins are widely used as model compounds of prosthetic groups of many biological molecules such as cytochromes, hemoglobin, myoglobin, catalases, etc. [5][6][7]. The modification of the porphyrin's core by replacement of the NH fragment of the pyrrole ring(s) by isoelectronic heteroatoms from the 16 th group of the periodic table, e.g.…”