The trans‐mer‐[(κ2‐N,S‐NS2C7H4)PR3Ru{κ3‐H,S,S′‐H2B (NS2C7H4)2}], (trans‐mer‐1 a: R=Cy; trans‐mer‐1 b: R=Ph) complexes are kinetically controlled products that upon thermolysis led to the formation of cis‐mer‐[(κ2‐N,S‐NS2C7H4)PR3Ru{κ3‐H,S,S′‐H2B(NS2C7H4)2}], (cis‐mer‐2 a: R=Cy; cis‐mer‐2 b: R=Ph) and cis‐fac‐[(κ2‐N,S‐NS2C7H4)PR3Ru{κ3‐H,S,S′‐H2B(NS2C7H4)2}], (cis‐fac‐3 a: R=Cy; cis‐fac‐3 b: R=Ph) along with complex cis‐[(κ2‐N,S‐NS2C7H4)2Ru(PPh3)2], (cis‐4). One of the main intentions of this study was to examine the flexibility of the borate and hemilabile N,S‐chelating mercapto‐benzothiazole ligands in adapting different spatial arrangements around metal center. Multinuclear spectroscopic analyses have been done to characterize all new complexes and the structures were further confirmed by single‐crystal X‐ray diffraction analysis. Further, Density Functional Theory (DFT) calculations were performed to provide an insight into the bonding of the complexes.