Ditantalum Hydride Complexes with Bridging (2,6-ⁱPr₂C₆H₃)NSiHPh Silanimine Ligands Resulting from PhSiH₃−Imido Ligand Coupling. A Combined Spectroscopic and Theoretical Investigation

Reactions of Hydrosilanes with Transition Metal Complexes and Characterization of the Products

“…36a The role of the bridging hydride in 2-10 was unequivocally determined by a neutron diffraction study. 36a The hydride in Cp*(OC) 2 (H)WdSi(H)C(SiMe 3 ) 3 (1-29a) also was bridging and consistent with DFT calculations for this silylene complex, 38a 33 Two dimers are produced, from addition of 1 or 2 equiv of PhSiH 3 . The products, 1-20a and 1-20b (major), are shown in eq 99.…”

“…For instance, the vanadium dimer, Cp* 2 H 2 Ta 2 (µ-ArNSiHPh) 2 (1-20b, Ar ) 2,6-i Pr 2 C 6 H 3 ), did not exhibit exchange of any hydrides in the temperature range from -60 to 95°C, 33 123 The complex 2-36c, Fe 2 (η-H 2 SiPh 2 )(edt)(CO) 2 (dppv) [edt ) ethanedithiolate; dppv ) cis-C 2 H 2 (PPh 2 ) 2 ], exhibited no evidence in the NMR spectral data for fluxional behavior over the temperature range -80 to 20°C. 95c…”

“…33 16 Hydrogen atoms were included in calculated idealized positions but not refined. 33 Table 3, footnote 46. 155a 22 Non-hydrogen atoms were refined anisotropically.…”

Dehydrosilylation of ArNHSiH3 with Ytterbium(II) Amide: Formation of a Dimeric Ytterbium(II) Silanimine Complex

“…[6a, f] These unsaturated silicon complexes, although very rare in number, have been shown to display interesting structural features and reactivity. [6] Inspired by these findings, we became interested in the investigation of primary aminosilanes with an HN À SiH 3 linkage in lanthanide chemistry, as the elimination of hydrogen may take place to give lanthanide silanimine complexes. In addition, primary silanes are normally much more reactive and may undergo multiple reactions involving the Si À H bonds, which may allow us to study the unexplored fate of agostic complexes.…”

Agostic NSiH⋅⋅⋅Mo Complexes: From Curiosity to Catalysis

“…The Mo1 À Si1 bond involving the agostic silyl group (2.634(1) ) is significantly longer than the Mo1 À Si2 bond involving the terminal silyl group (2.495(1) ), but is comparable with the MoÀSi bonds involving the agostic silyl groups in the related complexes 1 (2.646(1) ) and 2 a (2.668(1) ). The agostic hydride ligand is at a long Mo1À H1b distance of 1.92 (5) , whereas the Si1ÀH1b bond of 1.49(5) is normal.…”