Lucier, Bryan E. G., Tang, Joel A., Schurko, Robert W., Bowmaker, Graham A., Healy, Peter C. and Hanna, John V.. (2010) Solid-State Cu-65 and 31-P NMR spectroscopy of Bis(triphenylphosphine) copper species. Journal of Physical Chemistry C, Vol.114 (No.17). pp. 7949-7962. ISSN 1932-7447

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Abstract

Frequency-stepped ultrawideline (UW) Cu-65 solid-state NMR (SSNMR) experiments have been performed on a series of nine bis(triphenylphosphine) copper(I) species, with eight of these having an oxyanion-based ligand and one a borohydride ligand. These copper atoms reside in spherically asymmetric environments featuring two covalent Cu-P bonds and coordination from single bidentate ligands. The QCPMG pulse sequence was utilized in NMR experiments on all of the samples, along with the WURST-QCPMG sequence on select samples, to acquire UWNMR spectra of high quality. In all cases, large Cu-65 quadrupolar coupling constants (C-Q) between 40.8 and 51.7 MHz are observed, and are confirmed by NQR measurements. The immense quadrupolar interactions and their correspondingly large contributions to the central-transition powder patterns make accurate quantification of copper chemical shift anisotropy (CSA) difficult, though CSA effects are observed. H-1-P-31 CP/MAS NMR spectra reveal one-bond J-couplings, (1)J((65/63)cu, P-31) for all complexes, as well as the presence of residual dipolar coupling, which enables determinations of both the sign of C-Q and the orientation of the EFG tensor with respect to the Cu-P dipolar vector (both of which are unavailable from standard Cu-65 SSNMR experiments). The Cu-65 EFG parameters and (1)J((65/63)cu, P-31) coupling constants are sensitive to the local geometry and bond lengths about the Cu center. Ab initio calculations are used to confirm experimentally predicted orientations of the Cu EFG tensors, to predict experimental C-Q, eta(Q), and CS tensor values, and to aid in identifying relationships between the copper NMR parameters and molecular structures. This combination of experimental and theoretical NMR data enables the correlation of symmetry and local structure with copper NMR parameters, further extending the applicability of copper SSNMR spectroscopy to a wide variety of copper-containing systems.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry T Technology T Technology > TA Engineering (General). Civil engineering (General)
Divisions:	Faculty of Science > Physics
Journal or Publication Title:	Journal of Physical Chemistry C
Publisher:	American Chemical Society
ISSN:	1932-7447
Date:	6 May 2010
Volume:	Vol.114
Number:	No.17
Number of Pages:	14
Page Range:	pp. 7949-7962
Identification Number:	10.1021/jp907477m
Status:	Not Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Restricted or Subscription Access
Funder:	Natural Sciences and Engineering Research Council (NSERC, Canada), Canadian Foundation for Innovation, Ontario Innovation Trust, University of Windsor, Ontario Ministry of Research and Innovation, Centre for Catalysis and Materials Research (CCMR) at the University of Windsor, AINSE
Grant number:	06210
URI:	http://wrap.warwick.ac.uk/id/eprint/6030

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