Cyanato- and thiocyanato-substituted triangular clusters of molybdenum, [Mo₃S₄(dppe)₃X₃]⁺ (X = NCO⁻, NCS⁻; dppe = 1,2-bis(diphenylphosphino)ethane)

Abstract

Two pseudohalido-substituted cluster complexes, [Mo₃S₄(dppe)₃(NCS)₃]NCS (1) and [Mo₃S₄(dppe)₃(NCO)₃]Br (2) (dppe = 1,2-bis(diphenylphosphino)ethane), have been synthesized by substitution between [Mo₃S₄(dppe)₃Br₃]Br and potassium thiocyanate or sodium cyanate, respectively, in boiling acetonitrile. The compounds were characterized by IR-spectroscopy, elemental analysis, electrospray mass-spectrometry, and single-crystal X-ray diffraction analysis. Both compounds crystallize as toluene solvates (1·3C₆H₅CH₃ and 2·2.5C₆H₅CH₃) in space group with similar unit cell dimensions and adopt very similar molecular geometries. Both structures consist of discrete cluster cations [Mo₃S₄(dppe)₃X₃]⁺, NCS⁻ or Br⁻ anions, and solvate toluene molecules.

Keywords:

• Molybdenum
• Triangular clusters
• Chalcogenides
• Pseudohalides
• Mass-spectrometry
• Crystal structure

Acknowledgements

P.A.P. thanks Russian Scientific Foundation for financial support under grant [grant number 14-23-000-13]. M.Yu.A. thanks Russian Foundation for Basic Research for financial support under grants [grant number 12-03-33028], [grant number 13-03-01088]. The authors thank Dr Cristian Vicent Barrera (Universitat Jaume I, Castelló, Spain) for registration of mass spectra.