Nuclear magnetic resonance studies of some dichloro (pyridine 1

I. Metal-carbon .pi. bonding and the geometry of acetylene. A. C. Blizzard , D. P. Santry. Journal of the American Chemical Society 1968 90 (21), 5749...
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D. KAPLAN AND MILTOX URCHIN 1096 PHYLLIS TABLE V U q VALUESFOR PYRIDINE OBTAINED FROM SOLUTION WITH VARIOUSXXIOSSIN THE AXIAL POSITION^^^ DpY

Compound

Xi(py)nC12 Ni(pyhBrz Ni(py)d C101)2 cL All units are cm-1. See ref 1.

10,300 11,200 12,500 *ill solvents are CH2C11.

Ref C

C

c

d This work.

supported by nmr contact shift studies22of the complexes C O ( C ~ H ~ N(where ) ~ X ~X is chloride or bromide). As we go to the Clod- nickel complex, the bonding t o this anion should become more ionic resulting in a larger effective charge on the metal. This allows a stronger interaction of pyridine with the nickel ion, resulting in an even larger value for the Dq of pyridine as the covalency of the axial ligand decreases. However, in solids, the packing may also affect the environment of the thus meaningful trends cannot be evalu(22) For a more complete discussion of anion effects in bonding in transition metal complexes, see: B. R. Wayland and I