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Reactions of the mesityl(amidinato)tetrylenes E(  Bu 2 bzam)Mes (  Bu 2 bzam = N,N'-bis(tert-butyl)benzamidinate; Mes = mesityl; E = Ge (1 Ge ), Si (1 Si )) with the iridium precursors [Ir 2 (μ-Cl) 2 (η 4 -cod) 2 ] (cod = 1,5-cyclooctadiene) and [Ir 2 Cl 2 (μ-Cl) 2 (η 5 -Cp*) 2 ] (Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl) at room temperature led to simple coordination of the tetrylene in the case of the germylenes ([IrCl(η 4 -cod){κ 1 Ge-Ge(  Bu 2 bzam)Mes}] (2 Ge ) and [IrCl 2 (η 5 -Cp*){κ 1 Ge-Ge(  Bu 2 bzam)Mes}] (3 Ge ), respectively, but to cyclometallated products in the case of the silylenes ([IrHCl(η 4 -cod){κ 2 C,Si-Si(  Bu 2 bzam)CH 2 C 6 H 2 Me 2 }] (4 Si ) and [IrCl(η 5 -Cp*){κ 2 C,Si-Si(  Bu 2 bzam)CH 2 C 6 H 2 Me 2 }] (5 Si ), respectively. While the cyclometallation of the germylene ligand of the iridium(i) complex 2 Ge could not be achieved by heating this complex in toluene at 90 °C, a similar treatment of the iridium(iii) complex 3 Ge led to [IrCl(η 5 -Cp*){κ 2 C,Ge-Ge(  Bu 2 bzam)CH 2 C 6 H 2 Me 2 }] (5 Ge ), which is the germanium analogue of 5 Si . DFT calculations have shown that the mononuclear κ 1 E-tetrylene iridium(i) complexes [IrCl(η 4 -cod){κ 1 E-E(  Bu 2 bzam)Mes}] (E = Si, Ge; isolated only for E = Ge, 2 Ge ) should not participate as intermediates in the synthesis of the cyclometallated iridium(iii) derivatives [IrHCl(η 4 -cod){κ 2 C,E-E(  Bu 2 bzam)(CH 2 C 6 H 2 Me 2 )}] (E = Ge, Si; isolated only for E = Si, 4 Si ).

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Mesityl(amidinato)tetrylenes as ligands in iridium(<scp>i</scp>) and iridium(<scp>iii</scp>) complexes: siliconversusgermanium and simple κ1-coordinationversuscyclometallation

Mesityl(amidinato)tetrylenes as ligands in iridium(i) and iridium(iii) complexes: siliconversusgermanium and simple κ1-coordinationversuscyclometallation

Mesityl(amidinato)tetrylenes as ligands in iridium(i) and iridium(iii) complexes: siliconversusgermanium and simple κ¹-coordinationversuscyclometallation