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Iron cyclopentadienylcarbonyl complexes with azoles. I. Complexes of imidazoles and vicinal triazoles

✍ Scribed by A.N. Nesmeyanov; Yu.A. Belousov; V.N. Babin; O.G. Aleksandrov; Yu.T. Struchkov; N.S. Kochetkova


Publisher
Elsevier Science
Year
1977
Tongue
English
Weight
751 KB
Volume
23
Category
Article
ISSN
0020-1693

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✦ Synopsis


The reactions of halides, a-CsHSFe(CO)?X (X = Cl, Br, I), with sodium salts of some triazoles and imidazoles yield compounds of the composition n-C5-HsFe(COJ2L (L = heterocycle moiety). These complexes react with acids and complex anions in water to form the salts [n-C,H,Fe(CO),LHJ' A-(A-= anion). Stabilization of these salts is ensured by the formation of a hydrogen bond between the cation and anion parts (H-bonding contact ion pair) or between the cation and molecules of the solvent in the outer coordination sphere. The hydrogen bond is realized via the NH group of the heterocyclic ligands and the acceptor fragment of the outer sphere ligands. X-ray analysis of the benzimidazole complex [n-C,H,Fe(CO),-I-N(C,H~~)~~ B(GHs~*(CH&-0 showed that it has monoclinic crystals

, a = 13.626(l), b = 25.410(7), c = lO.O88(1)W, fl = 92.65(1)O, d, = 1.28, d,l, = 1.285 g/cm3, Z = 4, spatial group P2Jn. The compounds n-C,H,Fe(CO)zL-B(CeH,/3 have been isolated by decomposition of the salts [n-CsHS-Fe(COjzLH]'A-, where A-= B(C,H&, and LH = some triazoles and imidazoles.


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The diiodine basicity (a soft Lewis basicity) of 15 azoles (imidazoles, pyrazoles and triazoles) was measured by means of the formation constant of the diiodine-azole complexes in heptane at 298 K. The preferred sites of diiodine fixation are the nitrogens N-3 in imidazoles, N-2 in pyrazoles and N-4