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Molybdenum(VI) imido complexes: formation of [Mo(NPh)(S2CNR2)3]X and [Mo(NPh)(S2CNR2)2(μ-MoO4)]2 (R = Me, Et) from the reaction of [MoO2(S2CNR2)2] and PhNCO under aerobic conditions

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Abstract

Products from the thermolysis of PhNCO and [MoO2(S2CNR2)2] (R = Me, Et) are highly dependent upon the reaction conditions. When carried out in air, the major products are cations, [Mo(NPh)(S2CNR2)3]+, as shown by a crystal structure of [Mo(NPh)(S2CNEt2)3]2[Mo6O19]. Under rigorously anaerobic conditions, reaction of two equivalents of PhNCO with [MoO2(S2CNR2)2] affords [Mo(NPh)2(S2CNR2)2] as the major product. However, chloroform solutions of the bis(imido) complexes hydrolyze in air to afford [Mo(NPh)(S2CNR2)2(μ-MoO4)]2, in which molybdate groups bridge between molybdenum(VI) imido-bis(dithiocarbamate) centers. These results are placed in context of our earlier studies of these reactions that lead to the formation of oxo-disulfide [MoS2(NPh)(S2CNR2)2] and dimeric molybdenum(V) [MoO(μ-NPh)(S2CNR2)]2 complexes, thus allowing a full picture of these transformations to be established.

Graphical Abstract

Heating PhNCO with [MoO2(S2CNR2)2] in air gives [Mo(NPh)(S2CNR2)3]X (R = Me, Et), but when the reaction is carried out under anaerobic conditions, [Mo(NPh)2(S2CNR2)2] initially results, chloroform solutions of which hydrolyze in air to afford [Mo(NPh)(S2CNR2)2(μ-MoO4)]2.

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References

  1. Wigley DE (1994) Prog Inorg Chem 42:239

    Article  CAS  Google Scholar 

  2. Green MLH, Hogarth G, Konidaris PC, Mountford P (1990) J Organomet Chem 394:C9

    Article  CAS  Google Scholar 

  3. Green MLH, Hogarth G, Konidaris PC, Mountford P (1990) J Chem Soc Dalton Trans 3781

  4. Kolomnikov IS, Koreshkov Yu D, Lobeeva TS, Volpin ME (1970) J Chem Soc Chem Commun 1432

  5. Maatta EA (1984) Inorg Chem 23:2650

    Article  Google Scholar 

  6. Nielson AJ (1986) Inorg Synth 24:194

    Article  CAS  Google Scholar 

  7. Coffey TA, Forster GD, Hogarth G (1993) J Chem Soc Chem Commun 1524

  8. Coffey TA, Forster GD, Hogarth G (1996) J Chem Soc Dalton Trans 183

  9. Coffey TA, Forster GD, Hogarth G (1995) J Chem Soc Dalton Trans 2337

  10. Hogarth G, Richards I (2005) Inorg Chim Acta 358:707

    Article  CAS  Google Scholar 

  11. Forster GD, Hogarth G (1995) Polyhedron 14:1401

    Article  CAS  Google Scholar 

  12. Barrie P, Coffey TA, Forster GD, Hogarth G (1999) J Chem Soc Dalton Trans 4519

  13. Hogarth G, Richards I (2005) Dalton Trans 760

  14. Minelli M, Le Hoang M, Kraus M, Kucera G, Loertscher J, Reynolds M, Timm N, Chiang MY, Powell D (2002) Inorg Chem 41:5954

    Article  CAS  Google Scholar 

  15. Young CG, Boreham CJ, Broomhead JA (1983) J Chem Soc Dalton Trans 2135

  16. Maatta EA, Wentworth RAD (1979) Inorg Chem 18:2409

    Article  CAS  Google Scholar 

  17. Maatta EA, Wentworth RAD (1980) Inorg Chem 19:2597

    Article  CAS  Google Scholar 

  18. Coffey TA, Forster GD, Hogarth G (1998) Inorg Chim Acta 274:243

    Article  CAS  Google Scholar 

  19. Moore FW, Larson ML (1967) Inorg Chem 6:998

    Article  CAS  Google Scholar 

  20. (2001) Area detector control and data integration and reduction software. Brüker AXS, Madison, WI

  21. SADABS (1997) University of Göttingen, Göttingen, Germany

  22. Sheldrick GM (1990) Acta Crystallogr Sect A 46:467

    Article  Google Scholar 

  23. Sheldrick GM (1993) SHELXL, Program for crystal structure refinement. University of Göttingen, Göttingen, Germany

    Google Scholar 

  24. (2001) SHELXTL PLUS. Bruker AXS Inc., Madison, WI

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  1. Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, UK

    Graeme Hogarth & Idris Richards

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  1. Graeme Hogarth
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  2. Idris Richards
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Correspondence to Graeme Hogarth.

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Hogarth, G., Richards, I. Molybdenum(VI) imido complexes: formation of [Mo(NPh)(S2CNR2)3]X and [Mo(NPh)(S2CNR2)2(μ-MoO4)]2 (R = Me, Et) from the reaction of [MoO2(S2CNR2)2] and PhNCO under aerobic conditions. Transition Met Chem 35, 111–115 (2010). https://doi.org/10.1007/s11243-009-9302-0

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  • DOI: https://doi.org/10.1007/s11243-009-9302-0

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