Secondary Coordination Sphere Alkylation Promotes Cyclometalation.

Diphosphines have taken on a dominant role as supporting ligands in transition-metal chemistry. Here, we describe complexes of the type [Cp*Fe(diphosphine)(X)] (X = Cl, H) where for diphosphine = 1,2- bis (di-allylphosphino)ethane (tape), a Lewis-acidic secondary coordination sphere (SCS) was installed via allyl group hydroboration using dicyclohexylborane (HBCy 2 ). The resulting chloride complex, [Cp*Fe(P 2 B Cy 4 )(Cl)] (P 2 B Cy 4 = 1,2- bis (di(3-cyclohexylboranyl)propylphosphino)ethane), was treated with n -butyllithium (1-10 equiv), resulting incyclometalation at iron. This reactivity is contrasted with [Cp*Fe(d n ppe)(Cl)] (d n ppe = 1,2- bis (di- n -propylphosphino)ethane), whereby addition of n -butyllithium provides a mixture of products. Overall, cyclometalation is a common elementary transformation in organometallic chemistry; here we describe how this outcome is accessed in response to Lewis acid SCS incorporation.