Hydrosilylation of an Iron(IV) Nitride Complex

Abstract

The nitride ligand in iron(IV) complex PhB-(MesIm) 3 FeN reacts with excess H 3 SiPh to afford PhB-(MesIm) 3 Fe(μ-H) 3 (SiHPh) as the major product, which has been structurally and spectroscopically characterized. Bulkier silane H a SiPh 2 provides iron(II) amido complex PhB(MesIm) 3 FeN(H)-(SiHPh 2 ) as the initial product of the reaction, with excess H 2 SiPh 2 affording diamagnetic PhB(MesIm) 3 Fe(μ-H) 3 (SiPh 2 ) as the major product. Unobserved iron(II) hydride PhB(MesIm) 3 Fe−H is implicated as an intermediate in this reaction, as suggested by the results of the reaction between iron(II) amido PhB(MesIm) 3 FeN(H) t Bu and H 3 SiPh, which provides PhB(MesIm) 3 Fe(H)(μ-H) 2 (Si(NH t Bu)Ph) as the sole product.

Synthesis of Rhodium and Iridium Complexes Supported by Bis(indolylphosphino)silyl Pincer Ligation: Competitive N–H and C–H Bond Activation by an Ir(I) Species

“…The Ir–N3 distance of 1.997(5) Å is in the range of those observed for the anilido derivatives and the geometry at the amido nitrogen is once again planar. Such examples of coordinatively unsaturated late metal alkylamido hydride complexes are exceedingly rare. , …”

Isomerization Reactions in Anionic Mesoionic Carbene‐Borates and Control of Properties and Reactivities in the Resulting CoII Complexes through Agostic Interactions

“…Such ligands have proven to be unique in terms of their ability to support small-molecule activation at transition-metal centers, as well as for their propensity to stabilize unusual metal oxidation states. [23][24][25][26][27][28][29][30][31][32][33][34][35][36] 1,2,3-Triazol-5-ylidene-basedmesoionic carbenes (MICs) are ar elatively new addition to the larger class of NHCs ( Figure 1A). [37][38][39][40][41][42] In the past decade,metal complexes of MICs were shown to display excellent properties,e .g.…”

“…Borate‐based anionic N‐heterocyclic carbenes (NHCs) are well‐established as an important class of ligand [1–22] . Such ligands have proven to be unique in terms of their ability to support small‐molecule activation at transition‐metal centers, as well as for their propensity to stabilize unusual metal oxidation states [23–36] . 1,2,3‐Triazol‐5‐ylidene‐based mesoionic carbenes (MICs) are a relatively new addition to the larger class of NHCs (Figure 1 A).…”

Isomerization Reactions in Anionic Mesoionic Carbene-Borates and Control of Properties and Reactivities in the resulting CoII Complexes through Agostic Interactions

“…Such ligands have proven to be unique in terms of their ability to support small molecule activation at transition metal centers, as well as for their propensity to stabilize unusual metal oxidation states. [23][24][25][26][27][28][29][30][31][32][33][34][35][36] 1,2,3-Triazol-5-ylidene-based mesoionic carbenes (MICs) are a relatively new addition to the larger class of NHCs (Figure 1, A). [37][38][39][40][41][42] In the past decade, metal complexes of MICs were shown to display excellent properties, among others in homogeneous catalysis, [37][38][39][40][41][42] in redox switchable catalysis, [43][44][45] and in photochemistry.…”