A Bis-Cyclopentadienyl Ligand-Supported Di-Iron Trihydride Motif as a Synthon for Access to Heterobimetallic Trinuclear Complexes

Herein, we report the synthesis of a flexible bis-cyclopentadienyl ligand L (the doubly deprotonated form of H2L (1,3-bis(2,4-di-tert-butylcyclopentadienyldimethylsilyl)benzene)), demonstrating its ability to stabilize a series of di-iron hydrido complexes. Notably, this ligand facilitates the isolation of an unprecedented anionic cyclopentadienyl ligand-supported di-iron trihydride complex, LFe2(μ-H)3Li(THF) (2), functioning as a synthon for the [Fe2(μ-H)3]− core and providing access to heterobimetallic complexes 4–6 with coinage metals.


NMR characterizations for all compounds
. 1 H NMR spectrum of H2L in C6D6.

UV-vis spectra for all compounds
Single-crystal X-ray diffraction for complexes 1, 3-6 were performed on a Bruker APEX DUO diffractometer with APEX II 4K and multi-layer mirror monochromated Mo Kα radiation (λ = 0.71073 Å) at 200(2) K. Data collection and reduction were performed with Bruker APEX II software.All of nonhydrogen atoms are refined anisotropically.Hydrogen atoms attached to the carbons were fixed at calculated positions and refined using a riding mode.Multiple disordered solvent molecules were observed in the crystal structures of all complexes.Whenever possible, co-crystallizing solvent molecules were modeled.Otherwise, SQUEEZE was employed to treat diffuse solvent contribution in the voids.For complex 2, Single crystals data were collected on Rigaku XtaLABHyPix-Arc 150 diffractometer with Cu-Kα radiation (λ = 1.54178Å) at 100(10) K.The structure determinations and refinements were carried out using the SHELXS and SHELXL programs, respectively, on the Olex2 interface.The structures were solved using direct methods, which yielded the positions of all nonhydrogen atoms.Hydrogen atoms on carbons were placed in calculated positions in the final structure refinement.
Table S1.Comparison of selected bond lengths of complexes 2-6.

Table S1 .
Crystal data and structure refinement for LFe2(

Table S4 .
Crystal data and structure refinement for LFe2