Stereochemical Nonrigidity in Solid Zirconium and Hafnium Tetrakistetrahydroborates. Evidence for Two Dynamic Intramolecular Rearrangement Processes in Covalent Tridentate Tetrahydroborates

I. Ssuer Chuang, Tobin Jay Marks, William J. Kennelly, John R. Kolb

Research output: Contribution to journalArticlepeer-review

12 Scopus citations

Abstract

Proton nuclear magnetic resonance studies of stereochemical dynamics in Zr(BH4)4and Hf(BH4)4have been carried out in the solid state. Variable temperature investigations were conducted in both continuous wave and pulsed modes. Two intramolecular motional processes were identified for each complex and the nature of these processes was interpreted on the basis of effective second moment calculations in both diffusive and positional jump regimes. The higher temperature process is assigned to rapid intramolecular bridge-terminal hydrogen exchange, Ea(Zr)=5.2 ± 0.3 (ΔG⧧=8.1 at 214 K) 1; Ea(Hf)=8.4 ± 0.3 (ΔG⧧=7.3 at 200 K) kcal/mol. The lower temperature motion is suggested to involve rapid threefold rotation about the ligand M-B-H (terminal) axis with Ea(Zr)=5.4 ± 0.2 (ΔG⧧=4.3 at 124 K) 1; Ea(Hf)=4.6 ± 0.2 (ΔG⧧=4.4 at 133 K) kcal/mol.

Original languageEnglish (US)
Pages (from-to)7539-7545
Number of pages7
JournalJournal of the American Chemical Society
Volume99
Issue number23
DOIs
StatePublished - Jan 1 1977

ASJC Scopus subject areas

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

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