Estimating the wavenumber of terminal metal-hydride stretching vibrations of octahedral d6 transition metal complexes

This an accepted manuscript published by the American Chemical SocietyThe wavenumbers of 774 terminal hydride, infrared active, stretching modes of 478 distinct classes of structures of d6 octahedral complexes of Mn(I), Re(I), Fe(II), Ru(II), Os(II), Co(III), Rh(III), Ir(III) and Pt(IV) have been collected from the literature. A fair correlation (R2 0.95 with standard deviation 31 cm-1) is found for the data with the equation MHcalc = v0 + delta vt + delta vn where v0 is the base wavenumber for the metal ion in question, delta vt is the parameter of influence of the ligand trans to the hydride and delta vn is a correction for the charge of the complex [MHL5]n+. The introduction of a cis influence parameter has little effect on the correlation showing that the trans influence dominates in this case. The equation is useful in identifying anomalous data reported in the literature, validating future assignments of vMH, understanding better metal-hydride bonding, and possibly assisting in identifying superior hydride–based catalysts.RHM thanks NSERC Canada for a Discovery grant and Compute Canada for a resource allocation grant to access Sharcnet