Structural Chemistry of Lithium Hydrazides
- 1 February 1995
- journal article
- Published by Wiley in European Journal of Inorganic Chemistry
- Vol. 128 (2) , 105-113
- https://doi.org/10.1002/cber.19951280204
Abstract
Deprotonation of NH protons, of four diorgano‐, organo(trimethylsilyl)‐ and bis(trimethylsilyl)hydrazines by n‐butyllithium in hexane led to the following lithium hydrazides: [Et‐(Li)N‐N(H)Et]6, (1)6, [Me3Si(Li)N‐N(Li)SiMe3]4, (2)4, [Me3Si‐(Li)N‐N(Li)SiMe3 · (Me3Si)2N‐N(Li)SiMe3]2 (3)2, and [Ph‐(Li)N‐N(Li)SiMe3]4, (4)4, respectively. The structure determination by X‐ray methods at low temperature reveals butterfly‐shaped Li2N2 structural monomeric units which associate through “laddering” to the observed oligomers thereby generating penta‐ and hexacoordinated Li centers. N‐N bonds lengths of up to 1.556 Å suggest that negative charge accumulates at the nitrogen atoms of (1)6, (2)4, and (3)2. An amazing structure shows the red compound 4 where two Li ions are π‐sandwiched between two phenyl groups each. The compound can be looked at as a new type of a lithium lithiate complex, Li2[Li6N8Ph4(SiMe3)4], but short N‐C and N‐N bonds in the Li6N8 core indicate that its negative charge is transferred to the phenyl groups.Keywords
This publication has 30 references indexed in Scilit:
- Die Strukturen von zwei Lithiumhydraziden: Liegen Elektronenmangelbindungen vor?Angewandte Chemie, 1994
- Dilithium‐N,N′‐bis(trimethylsilyl)hydrazid und ein Hydrolyseprodukt side‐on und end‐on an N2−2‐ und O2−2‐gebundene Li‐KationenEuropean Journal of Inorganic Chemistry, 1994
- The First Structure of a Lithiated Cyanamide; Synthesis of (PhNCNLi · HMPA)n by Extrusion of N2 and S from 5‐Phenylamino‐1,2,3,4‐thiatriazole with Li Reagents and HMPAAngewandte Chemie International Edition in English, 1993
- Ein molekulares Heterometallamid mit hoher Moleküldynamik: Kreist das Lithiumatom?Angewandte Chemie, 1993
- Lithium Di‐tert‐butylmethylsilylhydrazide, a Hexamer with Li+ Ions Bound Side‐on and End‐onAngewandte Chemie International Edition in English, 1993
- [tert‐Butylcyanide · Lithium Bis(trimethylsilyl)amide]2, a Model of the Intermediate RCN. MR′ Complex Formed in Reactions of Cyanides RCN with Organometallic Compounds R′MAngewandte Chemie International Edition in English, 1993
- Anionic Rearrangement of Hydrazines. II.1 Isomers of Bis(organosilyl)hydrazines2Journal of the American Chemical Society, 1966
- A Novel Rearrangement of 1,2-Bis(trimethylsilyl)hydrazineJournal of the American Chemical Society, 1964
- The Molecular Structure of the Two Dimethylhydrazines by Electron DiffractionJournal of the American Chemical Society, 1948
- The Electron Diffraction Investigation of the Structure of Benzene, Pyridine, Pyrazine, Butadiene-1,3, Cyclopentadiene, Furan, Pyrrole, and ThiopheneJournal of the American Chemical Society, 1939