scholarly journals Estimating the Acidity of Transition Metal Hydride and Dihydrogen Complexes by Adding Ligand Acidity Constants

2014 ◽  
Vol 136 (5) ◽  
pp. 1948-1959 ◽  
Author(s):  
Robert H. Morris
Keyword(s):  
Transition Metal ◽  
Metal Hydride ◽  
Acidity Constants ◽  
Dihydrogen Complexes ◽  
Transition Metal Hydride

Localized-orbital locator (LOL) profiles of transition-metal hydride and dihydrogen complexes,

2009 ◽  
Vol 87 (7) ◽  
pp. 965-973 ◽  
Author(s):  
Heiko Jacobsen
Keyword(s):  
Transition Metal ◽  
Metal Hydride ◽  
Relativistic Effects ◽  
Kinetic Energy Density ◽  
Model Compounds ◽  
Dihydrogen Complexes ◽  
Different Types ◽  
Transition Metal Hydride ◽  
Localized Orbital ◽  
Hydride Ligands

A bond descriptor based on the kinetic-energy density, the localized-orbital locator (LOL), is used to characterize the nature of the chemical bond in transition-metal hydride and dihydrogen complexes. Cationic complexes of the iron triad [MH3(PMe3)4]+ (M = Fe, Ru, Os) serve as model compounds for transition-metal hydrogen bonding, since these complexes not only present examples for hydride as well as dihydrogen complexes, but for certain representatives, the two different types of metal–hydrogen bonds are realized within the same molecule. Both types of ligands show characteristic LOL profiles: (3,–3) Γ attractors in close vicinity to the H-atom for hydride ligands, and (3,–3) Γ attractors located between the two atoms for a dihydrogen ligand with νΓ-values of 0.8 and 0.9, respectively. In-between structures combine elements of the hydride and dihydrogen ligands. Relativistic effects on the relative stability of various isomers for the set of model compounds have been evaluated.

DFT methods applied to answer the question: how accurate is the ligand acidity constant method for estimating the pKa of transition metal hydride complexes MHXL4 when X is varied?

2018 ◽  
Vol 47 (8) ◽  
pp. 2739-2747 ◽  
Author(s):  
Jan P. Unsleber ◽  
Johannes Neugebauer ◽  
Robert H. Morris
Keyword(s):  
Transition Metal ◽  
Metal Hydride ◽  
Acidity Constant ◽  
Acidity Constants ◽  
Dft Methods ◽  
Hydride Complexes ◽  
Anionic Ligands ◽  
Transition Metal Hydride

Additive ligand acidity constants AL of anionic ligands are calculated for neutral hydrides of iron(ii), ruthenium(ii) and osmium(ii) with phosphine and carbonyl co-ligands; constant AL in green, more variable AL in red.

Sign in / Sign up

Export Citation Format

Share Document