The chemistry of radical-ligand complexes of the transition metals has developed into a vibrant field of research that spans from fundamental studies on the relationship between the chemical and electronic structures to applications in catalysis the chemical and electronic structure to application in catalysis and functional materials chemistry. In general, fine-tuning of the relevant properties relies on an increasingly diversifying pool of radical-proligand structures. Surprisingly, the variability of the conformational freedom and the number of distinct bonding modes supported by many radical proligands is limited. This work reports on the angular constraints and relative geometric alignment of metal and ligand orbitals as key parameters that render a series of chemically similar thiyl/thiolate complexes of platinum(II) electronically and spectroscopically distinct. The use of conformational flexible thiophenols as primary ligand scaffolds is essential to establishing a defined radical-ligand [(S-arene)2Pt(II)](center dot+) core whose electronic structure is modulated by a series of auxiliary coligands at platinum.