Jianping Guo

Addition reactions of bis(trimethylsilyl)methyl- and 1-azzallyl-lithium with cyanoamines into triazines or β-diketiminatolithium compounds

Abstract Reactions of bis(trimethylsilyl)methyl lithium reagent Li[CHR2] (R=SiMe3) and 1-azaallyllithium, [ LiN(R)C(Bu t )C HR]2 with cyanoamines R′CN (R′=Me2N, 1-piperidyl or o, p-pyridyl) yielded β-diketiminatolithiums (1, 2, 5, 7, 8) or symmetrically and mixed substituted triazines (3, 4, 6, 9, 10), respectively. The mechanistic pathways involve silicotropic rearrangements from C to N or N to N and an unusual elimination of Li[CHR2]. The complexes 1, 6, 7, and 10 had been characterized by X-Ray diffraction.

Bis{N-[(dimethyl­amino)dimethyl­silyl]-2,6-dimethyl­anilido-κ2N,N′}zinc(II)

The title zinc amide, [Zn(C12H21N2Si)2], which was synthxadesized by the metathetical reaction of [LiN(SiMe2NMe2)(2,6-Me2C6H3)]2 with zinc dichloride, has the Zn atom N,N′-chelated by the N-silylated anilide ligand in a square-planar environment. There are two independent molxadecules in the asymmetric unit; in both, the Zn—Namine bonds are longer than the Zn—Nanilide bonds.

Dichloridobis{N-[(dimethylamino)dimethylsilyl]-2,6-dimethylanilido-κ2N,N′}hafnium(IV)

The monomeric title zirconium(IV) compound, [Zr(C12H21N2Si)2Cl2], was prepared by the metathetical reaction of [LiN(SiMe2NMe2)(2,6-Me2C6H3)]2 with zirconium tetrachloride. The Zr atom is N,N0-chelated by the N-silylated anilido ligand. Along with two Cl atoms, the six-coordinated Zr atom demonstrates a highly distorted octahedral geometry. The two ligands around the Zr atom are arranged cis to each other and obey the C2 symmetry operation. That means the asymmetric unit consists of only half of the molecular compound and the complete molecule is generated by a twofold axis. The two ends of the N—Si—N chelating unit exhibit different affinities for the metal center. The Zr—Namino bond is longer than the Zr—Nanilido bond.

(1S*,2R*,4aS*,6aS*,6bR*,10S*,12aR*,14aS*)-10-Hydr-oxy-1,2,6a,6b,9,9,12a-hepta-methyl-perhydro-picene-4a,14a-carbolactone.

The title compound, C30H48O3, was extracted from the plant Dracocephalum rupestre Hance. The molecule contains five fused cyclohexane rings and one five-membered lactone ring. Intermolecular O—H⋯O hydrogen bonds between the hydroxyl and carbonyl groups link the molecules into chains along [010]. The absolute structure has not been determined.

Ammonium diphenyl­phosphinate monohydrate

In the title salt, NH4 +·C12H10O2P−·H2O, the ion pair and water molecule interact through hydrogen bonds to form a layer structure.

Bis[1,3-bis­(diphenyl­phosphinoylimino)isoindolinato-κ3O,N,O′]calcium(II)

In the title compound, [Ca(C32H24N3O2P2)2], the 1,3-bis(diphenylphosphinoylimino)isoindoline ligand adopts a tridentate coordination mode. The compound exhibits a distorted octahedral geometry. The Ca atom lies on a twofold rotation axis.

[Bis(trimethyl­silyl)meth­yl]chloro­(phen­yl)phosphine

The title compound, C13H24ClPSi2, was synthesized via the reaction of bisxad(trimethylxadsily)methylxadlithium and dichloroxadphenylxadphosphine. The coordination geometry around the P atom is distorted tetrahedral.

catena-Poly­[lithium(I)-μ-1-tert-butyl-3-(3-pyridyl)-N,N′-bis­(tri­methyl­silyl)propane-1,3-diiminato]

The title compound, [Li(C18H32N3Si2)]n, is a convenient ligand-transfer reagent for the synthesis of metal complexes of this β-diketiminate ligand. Lithium is coordinated by three N atoms: two are in the delocalized NCCCN fragment and one is from the pyridyl in an adjacent molxadecule. Owing to the coordination of lithium by the pyridyl N atom, the crystal structure displays a one-dimensional polymeric structure.