Plasticity of the Nickel(II) coordination environment in complexes with hemilabile phosphino thioether ligands

Charles W. MacHan, Alexander M. Spokoyny, Matthew R. Jones, Amy A. Sarjeant, Charlotte L. Stern, Chad A. Mirkin

Research output: Contribution to journalArticlepeer-review

12 Scopus citations

Abstract

A series of homoligated Ni(II) complexes formed from two phosphino thioether (P,S) chelating ligands has been synthesized and characterized. Interestingly, this included octahedral Ni(II) complexes which, unlike previously characterized d8 Rh(I), Pt(II), and Pd(II) analogues, exhibit in situ exchange processes centered around chloride ligand dissociation. This was verified and studied through the controlled abstraction from and introduction of chloride ions to this system, which showed that these processes proceed through complexes with square pyramidal, tetrahedral, and square planar geometries. These complexes were studied with a variety of characterization methods, including single-crystal X-ray diffraction studies, solution 31P{1H} NMR spectroscopy, UV-vis spectroscopy, and DFT calculations. A general set of synthetic procedures that involve the use of coordinating and noncoordinating counteranions, as well as different hemilabile ligands, to mediate geometry transformations are presented.

Original languageEnglish (US)
Pages (from-to)3023-3033
Number of pages11
JournalJournal of the American Chemical Society
Volume133
Issue number9
DOIs
StatePublished - Mar 9 2011

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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