The Insertion Reactions of GeCl₂ with Mono‐ and Bis‐κ²‐N,S‐Chelated Ru(II) Complexes

Abstract

The dual‐site insertion of GeCl2 into bis‐1,3‐N,S‐chelated ruthenium complexes, [(PPh3)2Ru{κ2‐N,S‐(L)2}], (cis‐1L1 and cis‐1L2; L = NC5H4S (L1); L = NC7H4S2 (L2)) has been investigated by using the electron‐rich behavior of these ruthenium systems. The treatment of cis‐1L1 and cis‐1L2 with GeCl2.dioxane led to the isolation of dual‐site GeCl2 inserted [(PPh3)2Ru{κ2‐Ge,S‐(GeCl2L)2}], (cis‐2L1 and cis‐2L2) and mono‐site GeCl2 inserted product [(PPh3)2{κ2‐Ge,S‐(GeCl2L)}Ru(κ2‐N,S‐L)], (trans‐3L1 and trans‐3L2). The cis‐2L1 and cis‐2L2 have two fused 5‐membered (RuGeNCS) rings, while the trans‐3L1 and trans‐3L2 have one 5‐membered (RuGeNCS) and one 4‐membered (RuNCS) ring. The molecular structure of cis‐2L1 shows that both the germanium centers have distorted tetrahedral geometry. Similarly, treatment of mono‐1,3‐N,S‐chelated ruthenium complex, [{κ2‐N,S‐(NS2C7H4)}Ru{κ3‐H,S,S‐H2B(NC7H4S2)2}PPh3], trans‐4 with GeCl2.dioxane yielded Ge‐inserted complex, [{κ2‐Ge,S‐(GeCl2NS2C7H4)}Ru{κ3‐H,S,S‐H2B (NC7H4S2)2}], (trans‐5). Further, to study the possibility of inserting GeCl2 into the Ge(II)‐S bond, we have made mercapto ligand functionalized germylenes, [{(iBu)2ATI}Ge (NC5H4S)] (6L1) and [{(iBu)2ATI}Ge(NC7H4S2)] (6L2).