Synthesis and structure of a hafnium silylamide complex and the chemical vapor deposition of HfxSi1−xO2 films

New UIII and UIV silylamides and an improved synthesis of NaN(SiMe2R)2 (R = Me, Ph)

“…This structure can be also be compared with a transition metal analogue as the crystal structure of [Hf{N 2.079(2) Å) [49]. Agostic interactions were not mentioned in the paper, but the same asymmetry in the N(SiMe 2 H) 2 ligands was seen in the tilting of the group (HfeNeSi angles of approximately 110 and 125 ) with one set of shorter Si/Hf distances (3.090e3.169 Å) and one longer set (3.361e3.410 Å) [49].…”

Silylamide Complexes of Chromium(II), Manganese(II), and Cobalt(II) Bearing the Ligands N(SiHMe2)2 and N(SiPhMe2)2

“…Complexes M[N(SiMe 3 ) 2 ] 2 (M = Fe, Co) and their donor adducts were successfully employed as homogeneous catalysts, e.g., for the hydrosilylation of carbonyl compounds, as well as to design single-molecule magnets . Transition metal silylamide complexes have also been used as molecular precursors for metals, metal alloys, carbides, nitrides, oxides, and silicates according to chemical vapor deposition , and ammonolysis techniques . More recently, complexes M[N(SiMe 3 ) 2 ] 2 , and in particular iron and cobalt derivatives, were comprehensively studied as precursors for magnetic nanoparticles. − …”

A homoleptic tetravalent cerium silylamide

“…1). The molecular structure shows a Ce(IV) centre adopting a distorted tetrahedral geometry with N-Ce-N angles in the range from 98.35(4)1 to 116.33(4)1 placing 2 in the middle of known redox-stable complexes Hf[N(SiHMe 2 ) 2 ] 4 (1021-1051) 12 and U[N(SiHMe 2 ) 2 ] 4 (991-1261). 13 The average Ce-N bond length for 2 is 2.247 Å comparing similarly to other known tetravalent silylamide complexes (Ce[N(SiMe 3 ) 2 ] 3 Cl: 2.217 Å, 7a Ce(L)[N(SiMe 3 ) 2 ] 2 Cl: 2.258 Å (L = OCMe 2 CH 2 (CNCH 2 CH 2 NDipp); Dipp = C 6 H 3 iPr 2 -2,6) 8 and {Ce[N(SiMe 3 ) 2 ] 2 (m-O)} 2 : 2.245 Å) 9 as well as to Ce(NCy 2 ) 4 (2.242 Å).…”