Reactivity of bulky Ln(II) amidinates towards P4, As4, and As4S4

The reduction of P-4, As-4 and As4S4 (realgar) with the sterically encumbered reductants [(DippForm)(2)Ln(thf)(2)] (Ln = Sm, Yb; Dipp-Form = {(2,6-(Pr2C6H3)-Pr-i)NC(H) = N(2,6-(Pr2C6H3)-Pr-i)}(-)) is reported. For the first time, purely f-element containing inverse inorganic sandwich complexes [{(DippForm)(2)Sm}(2)(mu(2)-eta(4):eta(4)-E-4)] (E = P, As), featuring a pi-aromatic cyclo [E-4](2-) middle deck, were obtained upon reaction with P-4 and As-4. The reaction with realgar leads to a cage disruption and the formation of the unusual species [{(DippForm)(DippForm-AsS2)}Ln(thf)]. The reactivity of divalent Ln amidinates towards main group molecules is in comparison to metallocenes faster, more efficient and thus significantly influenced by the ligand environment. Experimental results are supported by DFT calculations.