NMR Shifts, Orbitals, and M···H−X Bonding in d8 Square Planar Metal Complexes
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Abstract
We have investigated M···H−C interactions in d8 square planar Rh and Pt complexes involving different types of C−H bonds, as well as a M···H−N hydrogen-bonded complex, using a combination of DFT and “atoms-in-molecules” (AIM) theory. The AIM analysis shows that both M···H−C and M···H−N interactions in d8 square planar complexes are of a closed-shell, electrostatic nature, similar to protein backbone hydrogen bonds. However, at the shortest M···H distances, both interactions have partial covalence. We find no evidence for the involvement of dz2 orbitals in M···H−C interactions but do find evidence for the involvement of dxz/yz orbitals in M···H−C bonding. The DFT calculations reproduce well the experimental proton NMR chemical shifts, with a theory-versus-experiment correlation coefficient R2 = 0.985. There are large downfield 1H NMR chemical shift changes on metal bonding, accompanied by changes in shielding tensor orientations.
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