Syntheses and properties of cyclosilazanes and cyclocarbosilazanes

Synthesis and Diverse Transformations of a Dinitrogen Dititanium Hydride Complex Bearing Rigid Acridane‐Based PNP‐Pincer Ligands

“…Thef ormation of 13 could also be viewed as the formal insertion of two silylene units into the N=Nb ond in 2, standing in sharp contrast with the N 2 silylation reactions observed in other complexes [18,19,[41][42][43] and thus constituting the first example of the formation of acyclodisilylenediazane unit through dinitrogen functionalization. [44] Complex 13 was paramagnetic and exhibited as olution magnetic moment of 2.8(1) mBin[D 8 ]THF,inagreement with at riplet spin state of the Ti III species.S ingle crystals of 13 suitable for X-ray crystallographic studies were obtained from abenzene solution at room temperature.Itwas revealed that 13 possesses acyclodisilylenediazane unit, and each of the two nitrogen atoms is bonded to aT ia tom that bears at riflate ligand (Figure 11). Thew hole molecule is centrosymmetric, and the four-membered cyclodisilylenediazane unit [N-(SiHPh) 2 N] is nearly square planar with the ]N1-Si1-N1' and ]Si1-N1-Si1' angles of 88.80(1)8 8 and 91.…”

Silicon–Nitrogen Bond Formation via Heterodehydrocoupling and Catalytic N‐Silylation

“…Indoles and pyrroles can be N‐silylated via deprotonation by a strong base followed by salt metathesis with a tertiary chlorosilanes [8a, 16] . Poly(silazanes) may be synthesized through reaction of secondary chlorosilanes and NH 3 in the presence of metal hydrides [15] or by ring‐opening polymerization of cyclic silazanes [17] . These reactions are not ideal, generating salt or acidic waste.…”

“…[8a, 16] Poly(silazanes) may be synthesized through reaction of secondary chlorosilanes and NH 3 in the presence of metal hydrides [15] or by ring-opening polymerization of cyclic silazanes. [17] These reactions are not ideal, generating salt or acidic waste. Figure 1.…”

Synthesis and Diverse Transformations of a Dinitrogen Dititanium Hydride Complex Bearing Rigid Acridane‐Based PNP‐Pincer Ligands

“…Thef ormation of 13 could also be viewed as the formal insertion of two silylene units into the N=Nb ond in 2, standing in sharp contrast with the N 2 silylation reactions observed in other complexes [18,19,[41][42][43] and thus constituting the first example of the formation of acyclodisilylenediazane unit through dinitrogen functionalization. [44] Complex 13 was paramagnetic and exhibited as olution magnetic moment of 2.8(1) mBin[D 8 ]THF,inagreement with at riplet spin state of the Ti III species.S ingle crystals of 13 suitable for X-ray crystallographic studies were obtained from abenzene solution at room temperature.Itwas revealed that 13 possesses acyclodisilylenediazane unit, and each of the two nitrogen atoms is bonded to aT ia tom that bears at riflate ligand ( Figure 11). Thew hole molecule is centrosymmetric, and the four-membered cyclodisilylenediazane unit [N-(SiHPh) 2 N] is nearly square planar with the ]N1-Si1-N1' and ]Si1-N1-Si1' angles of 88.80(1)8 8 and 91.20(1)8 8,r espectively.T he Ti1 À N1 bond length in 13 (1.908(3) )i ss lightly shorter than that of the Ti1 À N1(amide) bond in 12 (2.080-(2) )and significantly longer than that of the Ti2 À N2(imide) in 12 (1.838(2) ).…”