10.1021/ja073238x.s001
Joel A. Tang
Joel A.
Tang
Bobby D. Ellis
Bobby D.
Ellis
Timothy H. Warren
Timothy H.
Warren
John V. Hanna
John V.
Hanna
Charles L. B. Macdonald
Charles
L. B. Macdonald
Robert W. Schurko
Robert W.
Schurko
Solid-State <sup>63</sup>Cu and <sup>65</sup>Cu NMR Spectroscopy of Inorganic and
Organometallic Copper(I) Complexes
American Chemical Society
2007
Cu sites
65 Cu NMR experiments
transition patterns
760 kHz
71.0 MHz
65 Cu NMR Spectroscopy
field gradient
CSA
Significant copper chemical shielding anisotropies
6.7 MHz
CS tensors
quadrupolar interactions result
pairs exhibit
NMR interaction tensor parameters
CQ
CP
EFG tensor orientations
1500 ppm
QCPMG
2007-10-31 00:00:00
Dataset
https://acs.figshare.com/articles/dataset/Solid_State_sup_63_sup_Cu_and_sup_65_sup_Cu_NMR_Spectroscopy_of_Inorganic_and_Organometallic_Copper_I_Complexes/2977495
Solid-state <sup>63</sup>Cu and <sup>65</sup>Cu NMR experiments have been conducted on a series of inorganic and
organometallic copper(I) complexes possessing a variety of spherically asymmetric two-, three-, and four-coordinate Cu coordination environments. Variations in structure and symmetry, and corresponding changes
in the electric field gradient (EFG) tensors, yield <sup>63/65</sup>Cu quadrupolar coupling constants (<i>C</i><sub>Q</sub>) ranging from
22.0 to 71.0 MHz for spherically asymmetric Cu sites. These large quadrupolar interactions result in spectra
featuring quadrupolar-dominated central transition patterns with breadths ranging from 760 kHz to 6.7 MHz.
Accordingly, Hahn-echo and/or QCPMG pulse sequences were applied in a frequency-stepped manner to
rapidly acquire high <i>S</i>/<i>N</i> powder patterns. Significant copper chemical shielding anisotropies (CSAs) are
also observed in some cases, ranging from 1000 to 1500 ppm. <sup>31</sup>P CP/MAS NMR spectra for complexes
featuring <sup>63/65</sup>Cu-<sup>31</sup>P spin pairs exhibit residual dipolar coupling and are simulated to determine both the
sign of <i>C</i><sub>Q</sub> and the EFG tensor orientations relative to the Cu−P bond axes. X-ray crystallographic data
and theoretical (Hartree−Fock and density functional theory) calculations of <sup>63/65</sup>Cu EFG and CS tensors
are utilized to examine the relationships between NMR interaction tensor parameters, the magnitudes and
orientations of the principal components, and molecular structure and symmetry.