Synthetic route to vanadium(III) dichalcogenidophosphinate complexes, V(S2PPh2)3 and V(Se2PPh2)3: A spectroscopic and structural comparative study with analogous complexes of chromium(III), Cr(E2PPh2)3 (E=S, Se)

Christine A. Phipps, Joanna M. Rosenberger, McKenzie M. Miller, Sean R. Parkin, Jessie L. Brown

Research output: Contribution to journalArticlepeer-review

Abstract

Addition of the potassium dichalcogenidodiphenylphosphinate salts, KE2PPh2 (E=S, Se), to either the THF solvate of vanadium(III) chloride or unsolvated chromium(III) chloride results in rapid ligand substitution and the formation of a series of closely-related trivalent, neutral mononuclear complexes, M(E2PPh2)3 (M=V, Cr; E=S, Se), isolated in modest to good yield. The metal dichalcogenidophosphinate complexes reported herein were characterized by IR, UV-vis, and 1H NMR spectroscopies, and their solid-state molecular structures were determined by single-crystal X-ray crystallography. Importantly, the comparative analysis includes the structural and spectroscopic studies of two rare V(III) dithio- and diseleno-phosphinate VE6 cores, as well as, two previously known CrE6 analogues. In the solid-state the title complexes exhibit trigonal distortion from octahedral with torsion angles ranging from 43(2) to 50.3(6)° and structural parameters consistent with ligation of progressively ‘softer’ chalcogen-donors.

Original languageEnglish
Pages (from-to)1182-1192
Number of pages11
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Volume647
Issue number11
DOIs
StatePublished - Jun 11 2021

Bibliographical note

Funding Information:
All synthetic work was performed at Transylvania University and financially supported by the David and Betty Jones Faculty Development Fund. X‐ray crystallography was performed at the X‐Ray Facility at the University of Kentucky and financially supported by the NSF MRI program, award CHE‐1625732. We thank A. J. Gaunt for their insightful comments and J. E. McDonald (in memoriam) for their encouragement of this work.

Publisher Copyright:
© 2020 Wiley-VCH GmbH

Keywords

  • chromium(III)
  • diphenyldiselenophosphinate complexes
  • diphenyldithiophosphinate complexes
  • vanadium(III)

ASJC Scopus subject areas

  • Inorganic Chemistry

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