Solid-state 139La and 15N NMR spectroscopy of lanthanum-containing metallocenes

A preliminary set of solid-state 139La and 15N NMR data for lanthanum-containing metallocenes is presented, including (C5H5)3La, (C5Me4H)3La, [(C5Me5)2La]+[BPh4]-, and 15N-enriched [(C5Me4H)2La(THF)]215N2. Broad 139La NMR spectra, with breadths ranging from 600 kHz to 2.5 MHz, were acquired with piecewise QCPMG techniques at 9.4 T. Simulations of the spectra reveal 139La quadrupolar coupling constants (CQ) between 44 and 105 MHz. In addition, the first NMR measurement of a nitrogen chemical shift (CS) tensor for dinitrogen bound side-on to a metal atom is reported for [(C5Me4H)2La(THF)]215N2. The 139La NMR parameters show remarkable sensitivity to changes in metallocene structure and can be interpreted in an intuitive manner. Preliminary RHF and DFT calculations of 139La electric field gradient (EFG) and nitrogen CS tensors are used to provide tensor orientations and to rationalize the origin of the NMR parameters in terms of molecular structure and symmetry. The sensitivity of 139La and 15N NMR tensor parameters to changes in structure and bonding should prove invaluable in future studies of noncrystalline and disordered systems. Copyright © 2006 American Chemical Society.