293741-72-7Relevant academic research and scientific papers
Neutral and anionic silyl hydride derivatives of the tantalum imido fragment Cp*(DippN=)Ta (Cp* = η5-C5Me5; Dipp = 2,6-iPr2C6H3). Reactive σ-bonds and intramolecular C-H bond act
Burckhardt, Urs,Casty, Gary L.,Gavenonis, John,Tilley, T. Don
, p. 3108 - 3122 (2008/10/08)
Reactive σ-bonds and intramolecular C-H bond activations which involves the silyl ligands were discussed. Nuclear magnetic resonance (NMR) and X-ray analysis were performed. Results showed that complexes of this type possess two different bonds which read
Ditantalum hydride complexes with bridging (2,6-iPr2C6H3)NSiHPh silanimine ligands resulting from PhSiH3-imido ligand coupling. A combined spectroscopic and theoretical investigation
Burckhardt, Urs,Casty, Gary L.,Tilley, T. Don,Woo, Tom K.,Rothlisberger, Ursula
, p. 3830 - 3841 (2008/10/08)
The preparation and characterization of two novel dinuclear tantalum hydride complexes featuring bridging silanimine ligands are reported. The reaction of Cp*(ArN double bond)Ta[Si(SiMe3)3]H (Cp* = η5-C5Me5; Ar = 2,6-iPr2C6H3) with PhSiH3 resulted in formation of [Cp*(ArN double bond)TaH(μ-H)]2 (4% yield), yellow, paramagnetic Cp*2(ArN double bond)Ta2H2(μ-ArNSiHPh) (1, 18% yield), and dark green, diamagnetic Cp*2Ta2H2(μ-ArNSiHPh)2 (2, 71% yield). For 1 and 2, X-ray structure determinations characterize the ArNSiHPh silanimine ligand as possessing a Si-N single bond. This is confirmed by molecular orbital calculations that provide an average bond order of 0.7 for the Si-N bond. The ArNSiHPh fragment is therefore best viewed as a bifunctional silyl-amido ligand. For diamagnetic complex 2, the X-ray analysis revealed a molecular structure possessing nearly exact 2-fold symmetry (the hydride ligands were not located), while NMR spectroscopy indicates that the two Cp*Ta(μ-ArNSiHPh) fragments in the molecule are chemically inequivalent. To analyze the structure and bonding in this compound, a theoretical study based on density functional theory and ab initio molecular dynamics was carried out. Calculations of the entire 140-atom dinuclear tantalum system confirm a structure with an asymmetric substitution of the two hydride ligands, with one terminal and one bridging. The paramagnetic compound 1 exhibits structural features that are similar to those for 2. For this complex, the spectroscopic data and density functional calculations are consistent with a structure featuring terminal and bridging hydride ligands.
