Solvent-free methylthiomethyllithium [LiCH2SMe]∞: solid state structure and thermal decomposition

Abstract

Solvent-free [LiCH2SMe]infinity forms a layer structure consisting of four- (Li2C2), five- (Li2CS2), and six-membered (Li2C2S2) rings in the solid state; the compound violently explodes upon heating to T=160+/-5 degrees C under an argon atmosphere.

Synthesis, Molecular Structure, and Physical Properties of the Complexes [{PhB(pz)2(CH2SMe)}2M] (M = MnII, FeII; pz = pyrazol‐1‐yl) Containing a Novel [N,N,S]‐Heteroscorpionate Ligand

“…[21] A clean and high-yielding synthesis protocol requires the use of donorfree Li[CH 2 SMe], [22] Figure S1 in the Supporting Information}.…”

Copper Complexes of Mono‐ and Ditopic [(Methylthio)methyl]borates: Missing Links and Linked Systems En Route to Copper Enzyme Models

“…For the selective introduction of one or two (methylthio)-methyl groups in the first reaction step we employed donorfree LiCH 2 SMe, [43] because, in our hands, it gave far better results than the corresponding TMEDA-adduct (TMEDA: tetramethylethylenediamine). The improvement in terms of selectivity and yield of 2 and 3 was so significant that it outweighed the hazards associated with working with donorfree LiCH 2 SMe (the compound violently explodes upon air contact [43] ). One advantage of the TMEDA-free reagent lies in its poor solubility in the reaction solvent (C 6 H 6 ) which guarantees low stationary concentrations of the nucleophile and makes it easier to control whether mono-(2) or disubstitution (3) takes place.…”

“…SMe 2 and BBr 3 are commercially available. PhBBr 2, [42,45] p-Me 3 Si-C 6 H 4 -BBr 2, [44,45] and LiCH 2 SMe [43] were synthesized following literature procedures.…”

“…(ladder-like structure; LiÀS = 2.531(5) [50] ), and the infinite network of solvent-free (methylthio)methyllithium (LiÀS = 2.443(13) /2.662(12) [43] ). The phenomenon of considerably shorter Li À N bonds to the h 1 -coordinating pyrazolyl rings compared to bonds between Li + and m-coordinating pyrazolyl donors has also been observed for (…”

[Li2{CH2S(O)Ph}2(TMEDA)2] – An α-sulfinyl-functionalized methyllithium carbenoid

“…The first-time isolation of a lithium halide carbenoid was done by Boche and co-workers [16] and, most recently, thermally stable ones were synthesized by Le Floch and co-workers [17] and Gessner and co-workers [18,19]. However, only in relatively few cases a carbenoid reactivity, as shown for Köbrich's carbenoids, was proven for sulfur-functionalized methyllithium compounds like the monomeric [LiCH 2 SPh(PMDTA)] [20] (PMDTA = N,N,N 0 ,N 0 ,N 00 -pentamethyldiethylenetriamine), the solvent-free methylthiomethyllithium [21], the threefold sulfur substituted compounds of the type [LiC(SAr) 3 ] (Ar = aryl) [22,23] and lithiated thioacetals [24]. A carbenoid reactivity of a sulfinyl-functionalized methyllithium compound of the type I (YR n = S(O)R) has not yet been described.…”