Antiferromagnetic complexes involving metal---metal bonds III. Synthesis, structure and magnetic properties of heterotrinuclear complexes of the type M(CO)5L (M = Cr, Mo and w) containing [(C5H5CrSCMe3)2S] as unusual antiferromagnetic ligand L |
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Authors: | A A Pasynskii I L Eremenko Yu V Rakitin B Orazsakhatov V M Novotortsev O G Ellert V T Kalinnikov |
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Institution: | N.S. Kurnakov Institute of General and Inorganic Chemistry, Academy of Sciences of the U.S.S.R., Leninskii Pr. 31, Moscow U.S.S.R.;Institute of Organo-Element Compounds, Academy of Sciences of the U.S.S.R., Vavilova st. 28, Moscow U.S.S.R. |
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Abstract: | Isostructural heterotrinuclear complexes (C5H5CrSCMe3)2S · M(CO)5 (II–IV) were isolated from photochemical reactions between the antiferromagnetic complex (C5H5CrSCMe3)2S (I) (with the Cr---Cr bond 2.689 Å long and with the exchange parameter −2J = 430 cm−1) and metal hexacarbonyls, M(CO)6, where M is Cr, Mo, or W. According to the X-ray structural data on III and IV, complex I plays the role of an unusual antiferromagnetic ligand L bound to M through the sulphide bridge (M–S 2.58(2) Å). Its geometry remains practically unaffected by the complex formation (the Cr---Cr bond length in III and IV is 2.73(1) Å). The exchange parameter, −2J (410, 440 and 440 cm−1 in II to IV, respectively), also shifts only insignificantly from that of I, which probably means that indirect exchange via the sulphide bridge in I is of minor importance compared with the direct Cr---Cr exchange. The Cr---Cr bond length may thus be correlated with the observed overall exchange coupling. |
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Keywords: | To whom correspondence should be addressed Present address: Organisch-Chemisches Institut Universität Zürich-Irchel Winterthurerstrasse 190 CH-8057 Zürich (Switzerland) |
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