Synthesis of Dinuclear Mo-Fe Hydride Complexes and Catalytic Silylation of N2

Abstract

Two transition-metal atoms bridged by hydrides may represent a useful structural motif for N₂ activation by molecular complexes and the enzyme active site. In this study, dinuclear Mo^IV -Fe^II complexes with bridging hydrides, Cp^R Mo(PMe₃ )(H)(μ-H)₃ FeCp* (2 a; Cp^R =Cp*=C₅ Me₅ , 2 b; Cp^R =C₅ Me₄ H), were synthesized via deprotonation of Cp^R Mo(PMe₃ )H₅ (1 a; Cp^R =Cp*, 1 b; Cp^R =C₅ Me₄ H) by Cp*FeN(SiMe₃ )₂ , and they were characterized by spectroscopy and crystallography. These Mo-Fe complexes reveal the shortest Mo-Fe distances ever reported (2.4005(3) Å for 2 a and 2.3952(3) Å for 2 b), and the Mo-Fe interactions were analyzed by computational studies. Removal of the terminal Mo-H hydride in 2 a-2 b by [Ph₃ C]⁺ in THF led to the formation of cationic THF adducts [Cp^R Mo(PMe₃ )(THF)(μ-H)₃ FeCp*]⁺ (3 a; Cp^R =Cp*, 3 b; Cp^R =C₅ Me₄ H). Further reaction of 3 a with LiPPh₂ gave rise to a phosphido-bridged complex Cp*Mo(PMe₃ )(μ-H)(μ-PPh₂ )FeCp* (4). A series of Mo-Fe complexes were subjected to catalytic silylation of N₂ in the presence of Na and Me₃ SiCl, furnishing up to 129±20 equiv of N(SiMe₃ )₃ per molecule of 2 b. Mechanism of the catalytic cycle was analyzed by DFT calculations.

Keywords: dinuclear complex; hydrides; iron; molybdenum; silylamine.