DFT calculations on the full catalytic cycle for manganese catalysed enantioselective hydrogenation of a selection of ketones have been carried out at the PBE0‐D3_PCM//RI‐BP86_PCMlevel. Mn complexes of an enantiomerically pure chiralP,N,Nligand have been found to be most reactive when adopting a facial coordination mode. The use of a new ligand with anortho‐substituted dimethylamino‐pyridine motif has been calculated to completely transform the levels of enantioselectivity possible for the hydrogenation of cyclic ketones relative to the first‐generation Mn catalysts.In silicoevaluation of substrates has been used to identify those likely to be reduced with high enantiomer ratios (er), and others that would exhibit less selectivity; good agreements were then found in experiments. Various cyclic ketones and some acetophenone derivatives were hydrogenated wither'sup to 99 : 1.

A range of modern density functional theory (DFT) functionals have been benchmarked against experimentally determined metal hydride bond strengths for three first-row TM hydride complexes. Geometries were found to be produced sufficiently accurately with RI-BP86-D3(PCM)/def2-SVP and further single-point calculations with PBE0-D3(PCM)/def2-TZVP were found to reproduce the experimental hydricity accurately, with a mean absolute deviation of 1.4 kcal/mol for the complexes studied.

Indanone derivatives can be directly converted to amino-indanes with high enantioselectivity using a manganese catalyst. Selectivity can be rationalised by DFT calculations.

A general and highly enantioselective method for the preparation of tetra‐substituted 3‐hydroxyphthalide esters via isothiourea‐catalysed acylative dynamic kinetic resolution (DKR) is reported. Using (2S,3R)‐HyperBTM (5 mol %) as the catalyst, the scope and limitations of this methodology have been extensively probed, with high enantioselectivity and good to excellent yields observed (>40 examples, up to 99 %, 99 : 1 er). Substitution of the aromatic core within the 3‐hydroxyphthalide skeleton, as well as aliphatic and aromatic substitution at C(3), is readily tolerated. A diverse range of anhydrides, including those from bioactive and pharmaceutically relevant acids, can also be used. The high enantioselectivity observed in this DKR process has been probed computationally, with a key substrate heteroatom donor O⋅⋅⋅acyl‐isothiouronium interaction identified through DFT analysis as necessary for enantiodiscrimination.

We present graphRC, a method for rapid transition state (TS) mode analysis using internal coordinates derived from molecular graphs. The imaginary mode of a TS describes the direction of atomic motion at the saddle point, providing a local approximation to the reaction coordinate, while Intrinsic Reaction Coordinate (IRC) and Quick Reaction Coordinate (QRC) calculations trace the full pathway to adjacent minima. In all cases, displacements are expressed in Cartesian coordinates and do not directly describe changes in bonding. By translating these into internal coordinate changes (bonds, angles, and dihedrals), graphRC provides chemical insight into the TS mode and reaction coordinate trajectories without prior knowledge of reactant and product structures. Molecular connectivity is determined using xyzgraph, a flexible graph builder validated across 4846 structures spanning 61 elements and 490 element-pair bond types, with close agreement to DFT-derived bonding. Initial validation on 16 diverse TS achieved 100% identification of bond changes, rotations, and inversions, with zero false positives compared to IRC and QRC connectivity. Across 395 TS covering organic, organometallic, and catalytic transformations, normal-mode analysis alone detects the primary bond change in every case, with high agreement to IRC-derived connectivity. This enables programmatic TS verification at a fraction of the cost of formal reaction coordinate calculations, complementing more rigorous methods with rapid, interpretable analysis.