Structural Study on Alkali‐Carboxylate Functionalized Late‐Transition Metal Bis(dithiocarbamate) Complexes

Abstract Lithium, sodium, and potassium derivatives of amino‐acid derived bis(dithiocarbamate) complexes of bivalent nickel, palladium, platinum, and copper are readily available by treatment of the carboxylic‐acid functionalized complexes with the respective alkali metal hydroxide. Representative derivatives of the types A 4 [M(L1) 2 ], A 2 [M(HL1) 2 ], A[M(HL1)(H 2 L1)] ( N ‐dithioato‐iminodiacetate, L1), and A 2 [M(L2,3) 2 ] ( N ‐dithioato‐ l ‐prolinate, L2, and ‐ N ‐benzylglycinate, L3; A=Li, Na, K; M=Ni, Pd, Pt, Cu) were isolated and characterized by spectroscopic and thermal methods. Six entries were accessible to single‐crystal X‐ray structure determination, revealing the presence of different coordination‐polymeric structures and hydrogen‐bonded assemblies comprising solvent‐separated cations in the solid state. While the transition metal always retains its all‐sulfur coordination with defined geometry, the alkali metals are structurally more flexible. The latter are usually coordinated by carboxylate and water, but additional interactions with sulfur donors are also relevant in some cases.