Reduction of K⁺ or Li⁺ in the Heterobimetallic Electride K⁺[LiN(SiMe₃)₂]e^–

Given their very negative redox potential (e.g., Li+ → Li(0), −3.04 V; K+ → K(0), −2.93 V), chemical reduction of Group-1 metal cations is one of the biggest challenges in inorganic chemistry: they are widely accepted as irreducible in the synthetic chemistry regime. Their reduction usually requires harsh electrochemical conditions. Herein we suggest a new strategy: via a heterobimetallic electride intermediate and using the nonbinding “free” electron as reductant. Based on our previously reported K+[LiN(SiMe3)2]e– heterobimetallic electride, we demonstrate the reducibility of both K+ and Li+ cations. Moreover, we find that external Lewis base ligands, namely tris[2-(dimethylamino)ethyl]amine (Me6Tren) or 2,2,2-cryptand, can exert a level of reducing selectivity by preferably binding to Li+ (Me6Tren) or K+ (2,2,2-cryptand), hence pushing the electron to the other cation

Monomeric lithium and sodium silylbenzyl complexes:syntheses, structures, and C=O bond olefination

Herein we report the syntheses, structures and reactivity studies of two new monomeric alkali metal silylbenzyl complexes stabilised by a tetradentate amine ligand, tris[2-(dimethylamino)ethyl]amine (Me6Tren). The two complexes, namely [MR′(Me6Tren)] (R′: CH(Ph)(SiMe3)) (2-Li: M = Li; 2-Na: M = Na), exhibit significant different coordination modes according to their metal identity (Li: σ-coordination; Na: π-coordination). Reactivity studies of 2-Li and 2-Na reveal that they are efficient in promoting a widely-used class of organic functional group interconversion: C[double bond, length as m-dash]O bond olefination of ketones, aldehydes and amides, to produce tri-substituted internal alkenes

trans-Dibromidobis(triphenyl­phosphane)platinum(II) chloro­form monosolvate

Both the platininum complex and the solvent mol­ecule of the title compound, [PtBr2(C18H15P)2]·CHCl3, are located on a twofold rotation axis. The CH unit and the Cl atoms of the CHCl3 mol­ecule are disordered over two equally occupied positions. The complex shows a trans square-planar geometry about the Pt atom

Lithium, sodium and potassium enolate aggregates and monomers:syntheses and structures

In this Article, we report the syntheses and comparative structural studies of lithium, sodium, and potassium anthracen-9-yl enolates, as their aggregates (Li, Na: hexamer; K: tetramer) and ligand-stabilized monomers (for Li and Na). The monomers add new members to the rare collection of group-1 metal monomeric enolates. Moreover, the series covers different group-1 metal cations (Li+, Na+ and K+) and aggregate sizes, allowing comparative structural studies to elucidate how the metal identity and aggregate size influence the enolate structure

cis-Dichloridobis(triisopropoxy­phosphine)­platinum(II)

The title compound, [PtCl2(C9H21O3P)2], was obtained from a solution of PtCl2(COD) (COD = 1,5-cyclooctadiene) and triisopropyl­phosphite in dichloro­methane. The complex features a Pt(II) atom coordinated by two Cl and two P atoms, yielding a slightly distorted cis square-planar geometry

A monomeric methyllithium complex:synthesis and structure

Methyllithium (MeLi) is the parent archetypal organolithium complex. MeLi exists as aggregates in solutions and solid states. Monomeric MeLi is postulated as a highly reactive intermediate and plays a vital role in understanding MeLi-mediated reactions but has not been isolated. Herein, we report the synthesis and structure of the first monomeric MeLi complex enabled by a new hexadentate neutral amine ligand

(Disulfur dinitrido)triphenyl­anti­mony(V)

The title compound, [Sb(C6H5)3(N2S2)], contains a molecular entity that is very similar to that of the known polymorph of Sb(S2N2)Ph3 [Kunkel et al. (1997 ▶). Z. Naturforsch. Teil B, 52, 193–198], differing only in the orientation of the phenyl rings. The bond order in the SNSN unit is S—N=S=N, consisting of one long S—N bond, an inter­mediate length N=S bond and a short S=N bond

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

Monomeric organolithium (LiR) complexes could provide enhanced Li–C bond reactivity and suggest mechanisms for a plethora of LiR-mediated reactions. They are highly sought-after but remain a synthetic challenge for organometallic chemists. In this work, we report the synthesis and characterisation of a monomeric (trimethylsilyl)methyl lithium complex, namely [Li(CH2SiMe3)(κ3-N,N′,N′′-Me6Tren)] (1), where Me6Tren is a tetradentate neutral amine ligand. The structure of 1 was comprehensively examined by single-crystal X-ray diffraction, variable temperature NMR spectroscopy and electron absorption spectroscopy. Complex 1 decomposes via ligand C–H and C–N activations to produce a Li amide complex 2. Preliminary reactivity studies of 1 reveal C[double bond, length as m-dash]O insertion and C–H activation reaction patterns.<br/

cis-Dichloridobis(dimethoxy­phenyl­phosphine)palladium(II)

The title compound, [PdCl2(C8H11O2P)2], has a comparable structure to those of related palladium dichloride complexes containing trimethyl phosphinite and methyl diphenyl phosphinite. The Pd atom is located on a crystallographic twofold rotation axis: thus, there is just one half-mol­ecule in the asymmetric unit. The structure is isomorphous with the platinum analogue cis-[PtCl2{P(OMe)2Ph}2]