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Investigation of structure and dynamics in the sodium metallocenes CpNa and CpNa·THF via solid‐state NMR, X‐ray diffraction and computational modelling
Author(s) -
Widdifield Cory M.,
Tang Joel A.,
Macdonald Charles L. B.,
Schurko Robert W.
Publication year - 2007
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.2124
Subject(s) - chemistry , nmr spectra database , powder diffraction , crystallography , tensor (intrinsic definition) , solid state nuclear magnetic resonance , diffraction , crystal (programming language) , sodium , anisotropy , analytical chemistry (journal) , spectral line , nuclear magnetic resonance , optics , chromatography , physics , geometry , mathematics , organic chemistry , astronomy , programming language , computer science
Solid‐state 23 Na NMR spectra of two organometallic complexes, cyclopentadienylsodium (CpNa) and the tetrahydrofuran (THF) solvate of CpNa (CpNa·THF), are presented. Analytical simulations of experimental spectra and calculated 23 Na electric‐field gradient (EFG) tensors confirm that both complexes are present in microcrystalline samples of CpNa recrystallized from THF. For the solvate, 23 Na NMR experiments at 9.4 T and 11.7 T elucidate sodium chemical shielding (CS) tensor parameters, and establish that the EFG and CS tensor frames are non‐coincident. Single‐crystal X‐ray diffraction (XRD) experiments are used to determine the crystal structure of CpNa·THF: Cmca ( a = 9.3242(15) Å, b = 20.611(3) Å, c = 9.8236(14) Å, α = β = γ = 90° , V = 1887.9(5)Å 3 , Z = 8). For CpNa, 23 Na NMR data acquired at multiple field strengths establish sodium CS tensor parameters more precisely than in previous reports. Variable‐temperature (VT) powder XRD (pXRD) experiments determine the temperature dependence of the CpNa unit cell parameters. The combination of 23 Na quadrupolar NMR parameters, pXRD data and calculations of 23 Na EFG tensors is used to examine various models of dynamic motion in the solid state. It is proposed that the sodium atom in CpNa undergoes an anisotropic, temperature‐dependent, low frequency motion within the ab crystallographic plane, in contrast with previous models. Copyright © 2007 John Wiley & Sons, Ltd.