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Updated: Jul 2, 2026
Accessing Valuable Ligand Supports for Transition Metals: A Modified, Intermediate Scale Preparation of 1,2,3,4,5-Pentamethylcyclopentadiene
Published on: March 20, 2017
Comparisons between yttrium and titanium N-heterocyclic carbene complexes in the search for early transition metal
Polly L Arnold1, Sergey Zlatogorsky, Natalie A Jones
1School of Chemistry, Joseph Black Building, University of Edinburgh, West Mains Road, Edinburgh, EH9 3JJ, United Kingdom. Polly.Arnold@ed.ac.uk
Abstract:
The d (0) yttrium N-heterocyclic carbene compound YL 3 (L = OCMe 2CH 2[C{N(CHCH)NPr ( i )}]) has been made and structurally characterized. It adopts a mer configuration of the three bidentate ligands. A comparison of this with the isostructural d (1) titanium complex TiL 3 is made in order to seek experimental evidence of a pi-bonding contribution to the M-C bond. This has been augmented by DFT calculations. Experimentally, the metal radius-corrected Ti-C distance is shorter than the Y-C distance, suggesting a pi-bonding contribution in the d (1) complex, but the computational data suggest that a shorter sigma bond might simply be formed by the more strongly polarizing titanium cation. From the potassium reduction of TiL(OPr ( i )) 3, only a byproduct arising from silicone grease activation was isolable, identified as a mixed-valent, multinuclear, d (0)/d (1) cluster [Ti (III)L 2{Pr ( i )OSiMe 2O}K 2OTi (IV)(OPr ( i )) 4] 2 in which the carbene ligands are bound to the Ti (III) centers in preference to Ti (IV), with longer Ti-C distances than those found in TiL 3.
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