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Closed Shell Heavier Tetrylidyne Complexes of Group 6 Metals

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Book cover Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands

Part of the book series: Springer Theses ((Springer Theses))

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Abstract

One of the ultimate goals of this work was to prepare open-shell tetrylidyne complexes featuring a tetrel-centered unpaired electron.

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Notes

  1. 1.

    Reactions were carried out in different solvents such as THF, fluorobenzene, chlorobenzene, DME, xylene starting from room temperature to boiling temperature of the corresponding solvents. Furthermore, some reactions were also carried out in the presence of LiBr or LiI. All the reactions were followed by IR and 1H NMR spectroscopy, which revealed the formation of a mixture of the 17VE radical 2-Mo and 2-W and some unknown compounds. Several attempts to isolate these unknown complexes in pure form were unsuccessful.

  2. 2.

    The DIAMOND plot of the compound 6-Mo is not depicted as it shows similar structural motif as 6-W, but selected bond lengths (Å) and angles (°) are presented in the brackets.

  3. 3.

    The NBO analysis was carried out at the RIJCOSX-B97-D3/TZVP level of theory by Dr. G. Schnakenburg.

  4. 4.

    The salt [(C5Me5)Si][B(C6F5)4] was prepared following a modified procedure, than that described by Jutzi et al., starting from SiX2(NHC) (X = Br, I; NHC = Idipp, SIdipp) as Si(II) source. M. I. Arz, personal communication.

  5. 5.

    The deviation of methyl groups from the plane of the C5 ring plane of Cp* substituent ranges from 0.4(2)° to 2.8(1)°.

  6. 6.

    For simplicity, the halotetrylenes will be presented as monomeric species in the entire dissertation, despite the fact that they forms dimer in the solid state.

  7. 7.

    Monitoring of the reaction by IR spectroscopy showed ~98% completion after 2 h without any further conversion occurring after prolonged heating.

  8. 8.

    This trend may also reflect the more pronounced bendeing at the tetrel centers in the Tp/Tp′-germylidyne complexes compared to the Cp/Cp*-germylidyne complexes.

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  1. Institute Für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universitä, Bonn, Nordrhein-Westfalen, Germany

    Priyabrata Ghana

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Ghana, P. (2019). Closed Shell Heavier Tetrylidyne Complexes of Group 6 Metals. In: Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands. Springer Theses. Springer, Cham. https://doi.org/10.1007/978-3-030-02625-7_2

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