A monomeric (trimethylsilyl)methyl lithium complex: synthesis, structure, decomposition and preliminary reactivity studies

Abstract

In this work, a rare monomeric organolithium complex was reported, stabilised by a neutral tetradentate amine ligand. Its structure and decomposition/reactivity were studied.

Versatile Coordination Modes of Multidentate Neutral Amine Ligands with Group 1 Metal Cations

“…In comparison, with the presence of a bulkier Li-CH 2 SiMe 3 group, one of the side arms decoordinates to form a four-coordinate distorted trigonal pyramidal geometry in [Li(CH 2 SiMe 3 )(κ 3 - N , N ′, N ′′- Me 6 Tren)] ( 4 ) ( Chart 3 ), where 4 was recently reported by us. 31 …”

“… a Data taken from ref ( 31 ). The Me 6 Tren ligand is in κ 4 - N , N ′, N ″, N ′′′ ( 1 ) and κ 3 - N , N ′, N ′′ ( 4 ) mode, respectively.…”

“… 17 − 20 Tetra -dentate amine ligands, such as tris -[2-(dimethylamino)ethyl]amine (Me 6 Tren), also has been used in Group 1 chemistry. 22 − 31 Efforts were also made to combine multidentate neutral amine donors and anionic donors, such as a cyclen-derived tetra -dentate (NNNN) macrocylic anionic ligand developed by Okuda and co-workers. 32 However, the bis -, tris - and tetra -dentate ligands could not provide sufficient kinetic protection for isolating more reactive species.…”

Elucidating Solution-State Coordination Modes of Multidentate Neutral Amine Ligands with Group-1 Metal Cations: Variable-Temperature NMR Studies

“… 8 Another bidentate diamine ligand, namely, (−)-Sparteine, was used to isolate the first monomeric tert -butyllithium complexes. 9 , 10 Tetradentate tris -[2-(dimethylamino)ethyl]amine (Me 6 TREN) was employed to synthesize a series of Group-1 metal benzyl complexes 11 and a (trimethylsilyl)methyllithium monomeric complex 12 and was applied in Group-1 metal catalysis. 13 Recently, we reported a new hexa -dentate amine ligand, namely, N , N ′, N″ - tris -(2- N -diethylaminoethyl)-1,4,7-triaza-cyclononane (DETAN), which enabled the isolation and characterization of the first monomeric complex of the parent organolithium reagent: methyllithium.…”

Mechanochemical Reduction and Doping of Cobalt (II,III) Oxide (Co3O4) by Lithium Metal: A Facile Route to LixCoyO Materials

“…However, this route has not been explored so far. In this context and based on our interest in lithium chemistry [23]- [25], we hypothesized that by introducing lithium metal as a reductant and a Li-ion source, and using mechanochemical methods to increase the reducibility of Co3O4, it is possible to deliver facile Co3O4 reduction and Li + doping in a one-pot manner. The findings are reported herein.…”