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.