Experimental and Theoretical Studies of Unusual Four-Membered Metallacycles from Reactions of Group 4 Metallocene Bis(trimethylsilyl)acetylene Complexes with the Sulfurdiimide Me3SiN=S=NSiMe3

Authors

  • Katharina Kaleta,

    1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany, Fax: +49-381-1281-51176
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  • Martin Ruhmann,

    1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany, Fax: +49-381-1281-51176
    2. Abteilung Anorganische Chemie, Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059 Rostock, Germany, Fax: +49-381-498-6382
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  • Oliver Theilmann,

    1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany, Fax: +49-381-1281-51176
    2. Abteilung Anorganische Chemie, Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059 Rostock, Germany, Fax: +49-381-498-6382
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  • Subhendu Roy,

    1. Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012, India
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  • Torsten Beweries,

    1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany, Fax: +49-381-1281-51176
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  • Perdita Arndt,

    1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany, Fax: +49-381-1281-51176
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  • Alexander Villinger,

    1. Abteilung Anorganische Chemie, Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059 Rostock, Germany, Fax: +49-381-498-6382
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  • Eluvathingal D. Jemmis,

    1. Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012, India
    2. Indian Institute of Science Education and Research Thiruvananthapuram, CET Campus, Thiruvananthapuram 695016, India, Fax: +91-471-259-7442
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  • Axel Schulz,

    1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany, Fax: +49-381-1281-51176
    2. Abteilung Anorganische Chemie, Institut für Chemie, Universität Rostock, Albert-Einstein-Str. 3a, 18059 Rostock, Germany, Fax: +49-381-498-6382
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  • Uwe Rosenthal

    1. Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Str. 29a, 18059 Rostock, Germany, Fax: +49-381-1281-51176
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  • Dedicated to Professor Bernhard Lücke on the occasion of his 75th birthday

Abstract

The use of the sulfurdiimide RN=S=NR′ (R = R′ = SiMe3, 3) in reactions with group 4 metallocene bis(trimethylsilyl)acetylene complexes of the type [Cp2M(L)(η2-Me3SiC2SiMe3)] (1: M = Ti, no L; 2: M = Zr, L = pyridine) has led to the formation of four-membered metallacycles 4M containing the group 4 metal, nitrogen and sulfur. DFT calculations performed on compound 4Ti indicate that this complex is best described as a σ-complex with cyclic delocalisation of the ring electrons. Moreover, pseudo-Jahn–Teller distortion plays a significant role in stabilising this complex.

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