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<p>The stability in the series of half-sandwich 5-(η<sup>5</sup>-cyclopentadienyl)-5-metalla-1,3,2,4-dithiadiazoles incorporating a first-row transition metal was investigated in function of the electron configuration of the M<sup>III</sup> metal centre, at the DFT/B3LYP level of theory. Taking 5-(η<sup>5</sup>-cyclopentadienyl)-5-cobalta-1,3,2,4-dithiadiazole or CpCoS<sub>2</sub>N<sub>2</sub>, the only known and experimentally available compound in the series, as a reference, calculated electronic, thermodynamic, and geometric properties were combined with molecular orbital (MO) diagrams to investigate the relative stabilities of the systems. The results indicate that the stability of CpCoS<sub>2</sub>N<sub>2</sub> is linked to a small (positive or even negative) charge on the metal, the occupation of the bonding MO involved in back donation, and the absence of electrons in high-lying antibonding MOs. Moving away from Co in either direction within the period leads to a decreased stability, except for CpVS<sub>2</sub>N<sub>2</sub>, which exhibits numerous stabilizing features similar to CpCoS<sub>2</sub>N<sub>2</sub>.</p>

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Understanding the effect of first-row transition metals on the structure and properties of cyclopentadienyl-stabilized 5-metalla-1,3,2,4-dithiadiazoles

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  • 发表日期：

    2025年7月26日

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  • Joseph Kfoury,
  • Frank Blockhuys,
  • Julianna Oláh

摘要

The stability in the series of half-sandwich 5-(η5-cyclopentadienyl)-5-metalla-1,3,2,4-dithiadiazoles incorporating a first-row transition metal was investigated in function of the electron configuration of the MIII metal centre, at the DFT/B3LYP level of theory. Taking 5-(η5-cyclopentadienyl)-5-cobalta-1,3,2,4-dithiadiazole or CpCoS2N2, the only known and experimentally available compound in the series, as a reference, calculated electronic, thermodynamic, and geometric properties were combined with molecular orbital (MO) diagrams to investigate the relative stabilities of the systems. The results indicate that the stability of CpCoS2N2 is linked to a small (positive or even negative) charge on the metal, the occupation of the bonding MO involved in back donation, and the absence of electrons in high-lying antibonding MOs. Moving away from Co in either direction within the period leads to a decreased stability, except for CpVS2N2, which exhibits numerous stabilizing features similar to CpCoS2N2.