Polylithium organic compounds: Syntheses and selected molecular structures

1,1,2,2-Tetramethyl-1,2-bis(phenylthiomethyl)disilane, a Flexible Ligand for the Construction of Macrocyclic, Mesocyclic, and Bridged Dithioether Complexes. Synthesis of the Bis-silylated OlefinsZ-(PhSCH2)Me2SiC(H)C(Ar)SiMe2(CH2SPh) by Catalytic Activation of the Si−Si Bond

“…In the context of our interest on organosilicon compounds − and transition metal silyl complexes, − we have recently prepared a series of organosilanes functionalized by phenylthiomethyl substituents such as Ph 2 Si(PhSCH 2 ) 2 or Me(H)Si(PhSCH 2 ) 2 and coordinated these ligands via their thioether function or via a covalent M−Si bond on Pt and Re . In light of a potential application for bis-silylation reactions, we have now extended our research on the compound 1,1,2,2-tetramethyl-1,2-bis(diphenylthiomethyl)disilane ( 1 ).…”

A Monolithiated and Its Related 1,3-Dilithiated Allylsilane: Syntheses, Crystal Structures, and Reactivity

“…Herein we report the crystal structure of the tetrameric monolithiated allylsilane ( 2 ) 4 and the first crystal structure of a 1,3-dilithiated allyl compound ( 3 ) 6 . This analysis supplies vital structural information on the structure-determining principles of allyllithium compounds without external coordinating additives and represents the first examples of allyllithiums with only one donating ligand at lithium . The reactivity profile of the lithiated systems 2 and 3 strongly depends on the solvents and electrophiles used in trapping reactions and can be rationalized on the basis of the observed molecular structures for 2 and 3 in combination with quantum chemical studies.…”

Structural Characterization and Dynamic Solution Behavior of the Disodio and Lithio−Sodio Geminal Organodimetallics [{{Ph2P(Me3Si)N}2CNa2}2] and [{{Ph2P(Me3Si)N}2CLiNa}2]

“…Attempts at characterizing these complexes to gain an understanding of their bonding and reactivity has met with limited success, due to a combination of their metastability and poor solubility in many instances. A good deal of attention has been focused on the dilithio derivatives; however, only three crystal structures of unadulterated dilithiated geminal carbanions have been reported, namely [{{Ph 2 P(Me 3 Si)N} 2 CLi 2 } 2 ] ( 1 ), [{Me 3 Si(NC)CLi 2 } 12 ·6Et 2 O] ( 2 ), and the polymer 9,9-dilithiofluorene ( 3 ). A handful of mixed-anion complexes containing both a dilithio geminal dianion and either a monometalated ligand fragment or an Li 2 O unit are also known .…”