Syntheses, Structures and Reactivity of Electron‐Rich Fe and Ru Complexes with the New Pentadentate Ligand Et 2 NpyS 4 −H 2 {4‐(Diethylamino)2,6‐bis[(2‐mercaptophenyl)thiomethyl]pyridine}

Autor: Dieter Sellmann, Shaban Y. Shaban, Frank W. Heinemann
Rok vydání: 2004
Předmět:
Zdroj: European Journal of Inorganic Chemistry. 2004:4591-4601
ISSN: 1099-0682
1434-1948
Popis: The new pentadentate thioether thiolate ligand Et2NpyS42− {= 4-(diethylamino)-2,6-bis[(2-mercaptophenyl)thiomethyl]pyridine(2−)} has been synthesised from dimethyl 4-bromopyridine-2,6-dicarboxylate by treatment with Et2NH followed by reduction and tosylation. The tosylated product was subsequently used for the template alkylation of [Ni(S2C6H4)2]2− to give [{Ni(Et2NpyS4)}2] (4). Acidic hydrolysis of 4 resulted in the formation of the ligand Et2NpyS4−H2·HCl (5). The dianion Et2NpyS42− reacted with FeCl2·H2O to afford the dinuclear high-spin species [{Fe(Et2NpyS4)}2] (6) [μeff (297 K) = 5.15 μB]. Aerial oxidation of dinuclear 6 afforded the sulfinato complex [{Fe(Et2NpyS4−O2)}2] (7). Complex 6 proved to be a good precursor for the syntheses of [Fe(L)(Et2NpyS4)] [L = CO (8), CNCy (9), NO (11) and N2H4 (12)] and [Fe(NO)(Et2NpyS4)]BF4 (10). Protonation or alkylation of the thiolate donor atoms resulted in a series of complexes [Fe(CO)(Et2NpyS4−R)]BF4 [R = H (8a), Et (8b)] and [Fe(CO)(Et2NpyS4−Et2)](BF4)2 (8c) but no labilisation of the Fe−CO bond was observed. Only in complex 8 could the CO coligand be exchanged by NO+ to give [Fe(NO)(Et2NpyS4)]BF4 (10). Reduction of 10 using N2H4, NH3 or N3− afforded the 19 valence electron species [Fe(NO)(Et2NpyS4)] (11). [Ru(NO)(Et2NpyS4)]Br (13) was synthesised by template alkylation of Bu4N[Ru(NO)(S2C6H4)2] using Et2Npy(CH2Br)2 (3). Under reducing conditions, 13 releases the NO coligand to give [{Ru(Et2NpyS4)}2] (14), while in the presence of N2H4, [Ru(N2H4)(Et2NpyS4)] (15) was formed. The complexes were well characterised including the solid-state structures in most cases. X-ray structural analyses of 7, 8, 9, 10, 12 and 15 revealed that all complexes exhibit trans-thiolate donors irrespective of the σ−π- or σ-ligand character of L. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
Databáze: OpenAIRE
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