Pentamethyl- And 1,2,4-tri(tert-butyl)cyclopentadienyl containing p-block complexes - differences and similarities

The sterically encumbered cyclopentadienyl ligand 1,2,4-(Me₃C)₃C₅H₂(Cp′′′) was used to stabilize efficiently the main group metals of Al, Ga, In, Ge and Sn, respectively. The σ-bonded gallium compounds [η¹-Cp′′′Ga(μ-X)X]₂(X = Cl,2; X = I,3) and indium compound [η¹-Cp′′′In(μ-Br)ⁿBu]₂(7) exhibit dimers through halogen bridges. Reduction of2with 2 equivalents of KC₈leads almost to the same amount of η¹-Cp′′′Ga(THF)Cl₂(4) and η⁵-Cp′′′Ga (5), respectively. The exception is compound5, which is obtained by reducing2or3with 4 equivalents of KC₈. Compound5as Lewis base reacts with GaI₃readily forming the Lewis acid-base adduct product η⁵-Cp′′′Ga → GaI₃(6). Moreover, compounds with the Cp′′′ ligand stabilize heavier low-valent group 14 elements for example [η⁵-Cp′′′E^II]⁺[E^IICl₃]⁻(E = Ge8, Sn9), which are π-bonded ionic compounds that possess a low-valent cation and an anion. In the cation of [η⁵-Cp′′′E^II]⁺, the Cp′′′ ligand adopts an η⁵-coordination mode with germanium and tin, respectively, which present half-sandwich complexes. While the E^IIfragment interacts with five π electrons from the Cp′′′ unit to generate an electron-octet arrangement at the respective element. All new reported structures are comparing well with the corresponding compounds containing the pentamethylcyclopentadienyl (Cp*) ligand.