American Chemical Society
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Acetylenic Carbon-13 Chemical Shift Tensors for Diphenylacetylene and (η2-Diphenylacetylene)Pt(PPh3)2:  A Solid-State NMR and Theoretical Study

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journal contribution
posted on 2006-03-20, 00:00 authored by Kristopher J. Harris, Guy M. Bernard, Chris McDonald, Robert McDonald, Michael J. Ferguson, Roderick E. Wasylishen
The structure of (η2-diphenylacetylene)Pt(PPh3) 2, as well as those of its dichloromethane and benzene solvates, is determined via X-ray crystallography. An investigation of the chemical shift (CS) tensors of the 13C-labeled carbons in Ph13C⋮13CPh and (η2-Ph13C⋮13CPh)Pt(PPh3)2·(C6H6) is carried out via analysis of 13C NMR spectra from stationary solid samples. The principal components of the CS tensors as well as their orientations with respect to the 13C,13C internuclear vector are determined. DFT calculations of these CS tensors are in close agreement with the experimental values. For diphenylacetylene (tolane), the orientations and principal-component magnitudes of the alkynyl carbon CS tensors are comparable to those for other alkynyl carbons, although the CS tensor is not axially symmetric in this case. Coordination to platinum causes a change in the CS tensor orientation and a net increase in the isotropic chemical shift, resulting from a significant increase in two principal components (δ11 and δ33) while the third (δ22) decreases only slightly. The measured carbon CS tensors in the platinum complex bear a striking similarity to those of the alkenyl carbons in trans-Ph(H)CC(H)Ph, and a short theoretical discussion of these observations is presented.