Abstract
Here, we present the light-driven reactions of [Re(η(7)-C(7)H(7))(η(5)-C(7)H(9))](+) (1(+)) with nitriles, phosphines, and isocyanides, which are added to 1(+) via a ring slippage of the tropylium cation from η(7) to η(3), forming [Re(η(3)-C(7)H(7))(η(5)-C(7)H(9))(L)(2)](+) (L= acetonitrile 2(+); 2-phenylacetonitrile 3(+); 1,3,5-triaza-5-phosphoadamantane (PTA) 4(+); tert-butyl isocyanide 6(+); benzyl isocyanide 7(+)) and [Re(η(3)-C(7)H(7))(η(5)-C(7)H(9))(L)](+) with L = (ethane-1,2-diyl)bis(diphenylphosphane) (dppe) 5(+). To compare the reactivities of rhenium and technetium, we also investigated the synthesis of [(99)Tc(η(6)-C(10)H(8))(2)](+), its substitution of naphthalene with cyclohepta-1,3,5-triene to obtain [(99)Tc(η(7)-C(7)H(7))(η(5)-C(7)H(9))](+), and its reactivity (or lack thereof) with light.