Synthesis, Reactivity, and Complexation with Fe(0) of a Tight‐bite Bis(N‐heterocyclic silylene)

Abstract

The synthesis, reactivity, and complexation with Fe(0) precursor of a tight‐bite bis(N‐heterocyclic silylene) (bis(NHSi)) ligand 1 are reported. The reaction of 1 with p‐toluidine led to the activation of both N–H bonds across Si(II) atoms to afford a rare four‐membered heterocyclic cyclodisilazane 2, with hydride substituents attached to five‐coordinate Si atoms. A 1:2 reaction of 1 with Fe(CO)5 led to an intriguing dinuclear complex 3 featuring a five‐membered (N‐Si‐Fe‐Fe‐Si) ring with a Fe–Fe bond distance of 2.6892(13) Å. All compounds (1‐3) were thoroughly characterized by various spectro­scopic methods and X‐ray diffraction studies conclusively established their molecular structures. DFT calculations were carried out to shed light on bonding and energetic aspects in 1‐3.

A Bis(silylene)silole – synthesis, properties and reactivity

“…Since the first report on their synthesis by H. Roesky and coworkers in 2006, 3 their use as stabilizing ligands in main group and transition metal chemistry has strongly influenced the area of small molecule and bond activation. 4–7 In this respect the work of Driess and coworkers is of particular interest. 8–13 This group developed a series of bissilylenes A–G (Fig.…”