Synthesis and structure of new compounds with Pt–Ga bonds: Insertion of the bulky gallium (I) bisimidinate Ga(DDP) into Pt–Cl bond

[CpArNi{Ga(nacnac)}]: An Open-Shell Nickel(I) Complex Supported by a Gallium(I) Carbenoid (CpAr = C5(C6H4-4-Et)5, nacnac = HC[C(Me)N-(C6H3)-2,6-iPr2]2)

“…Low-valent organyl gallium species of the general type Ga-R (R = C 5 Me 5 {= Cp*}, C­(SiMe 3 ) 3 , terphenyl, nacnac, and related ligands) have been widely used as supporting ligands for metal-to-metal bonded complexes and clusters. − Among these, Ga­(nacnac), having a bulky nacnac ligand on gallium, has drawn special attention due to its ability to stabilize coordinately unsaturated metal complexes, such as [L 2 NiGa­(nacnac)] (L = C 2 H 4 , styrene; L 2 = 1,1,3,3-tetramethyl 1,3-divinyldisiloxane (dvds); Figure ). , Several other 18 VE electron Ni–Ga­(nacnac) complexes such as [L 2 NiGa­(nacnac)] (L = CO; L 3 = 1,5,9-cyclododecatriene (CDT); Figure ) were obtained by ligand substitution reactions. ,, Interestingly, Ga­(nacnac) can also insert into metal halide bonds, leading to M–Ga bonded complexes, although only a few examples are known involving transition metals. − The reaction with [AuCl­(PPh 3 )] gives the linear complexes [Au­{GaCl­(nacnac)}­(PPh 3 )] and [Au­{Ga­(nacnac)}­{GaCl­(nacnac)}] . A unique observation is the reaction of [RhCl­(PPh 3 ) 3 ] with Ga­(nacnac), which gave the “frozen-insertion intermediate” [Rh­(μ-Cl)­Ga­(nacnac)­(PPh 3 ) 2 ] …”