Lithium Solvation Research Articles

ChemInform Abstract: Structural Characterization of the Solvate Complexes of the Lithium Salts of Diorganophosphides and Phosphinideneborates. A Pathway to Phosphorus‐Boron Double Bonds.

Abstract The structures of several solvated lithium diorganophosphides are described. These may take a variety of structures including chain-like polymers with alternating Li+ and PR2 − groups, dimeric species with PR2 − groups bridging two Li+ ions or mononuclear species having terminal −PR2 groups which have pyramidal geometries at phosphorus. The Li+ ions in all structures are solvated by either THF or Et2O bases. Separation of the Li+ can be effected using 12-crown-4 to coordinate Li+ as [Li(12-crown-4)2]+ affording free [PR2]− counterions. An extension of these techniques has led to the synthesis of the first compounds which have B-P double bonds. These are the compounds [Li(Et2O)2PRBMes2] and [Li(12-crown-4)2][PRBMes2](R=Ph, C6H11,Mes) which have B-P bond lengths of 1.82 – 1.83A.

ChemInform Abstract: Isolation and Structural Characterization of the Solvated Lithium Salts of the Main Group 5 Anions (EPh2)‐ (E: N, P, As, or Sb) and (Sb3Ph4)‐.

AbstractNHPh2 or SbHPh2 in Et2O react with BuLi in hexane after addition of 12‐crown‐4 in THF to give the complexes (I) or (V).

Structural Characterization of the Solvate Complexes of the Lithium Salts of Diorganophosphides and Phosphinideneborates; A Pathway to Phosphorus-Boron Double Bonds

Abstract The structures of several solvated lithium diorganophosphides are described. These may take a variety of structures including chain-like polymers with alternating Li+ and PR2 − groups, dimeric species with PR2 − groups bridging two Li+ ions or mononuclear species having terminal −PR2 groups which have pyramidal geometries at phosphorus. The Li+ ions in all structures are solvated by either THF or Et2O bases. Separation of the Li+ can be effected using 12-crown-4 to coordinate Li+ as [Li(12-crown-4)2]+ affording free [PR2]− counterions. An extension of these techniques has led to the synthesis of the first compounds which have B-P double bonds. These are the compounds [Li(Et2O)2PRBMes2] and [Li(12-crown-4)2][PRBMes2](R=Ph, C6H11,Mes) which have B-P bond lengths of 1.82 – 1.83A.

Formation of phosphonoacetate carbanions by lithiated bases or by the conjunction of a lithium salt and an amine: structural study of intermediate species

In THF, the anionic species (2) formed from methyl diethylphosphonoacetate (1b) by the action of Li bases coexist as aggregates (2A) and externally solvated monomeric ion pair (2M), while in CH3CN triple ions (2T) and small amounts of free ions (2–) are also characterized. When (1b) is in slight excess, relative to the lithiated base, these four species coexist in both solvents, together with other species (I). From n.m.r. and i.r. data, it appears that the intermediate species (I) include a neutral phosphonate (1b) moiety, as a Li+ cation bidentate ligand, the two other lithium solvation sites being occupied either by (2–), or by (1b) as a monodentate and a solvent molecule, or else by two solvent molecules. The structure of (1b) in this intermediate species is strongly perturbed as deduced from variations in 31P and 13C carbonyl shifts as well as that of νco. Furthermore, a fast proton exchange takes place between the anionic species (2) and free (1b) as shown by 1H n.m.r., but (I) does not participate in this exchange phenomenon. When (2) is formed by action of diazabicycloundecene (DBU) in the presence of LiCl, aggregates (2A), monomeric ion pari (2M), and small amounts of (2T) as well as two intermediate species (I) are characterized by i.r. or 31P n.m.r. spectroscopy. The role of DBU is manifold: it deaggregates LiCl or (2A), it deprotonates (1b) within (I), and it facilitates proton exchange between (2) and (1b), the relative importance of such effects depending upon the DBU concentration.

Reactions of platinum(II) acetylides with organolithium compounds: formation of lithium-bridged dinuclear platinum(II) complexes and of triorganoplatinate(II) complexes: crystal structure of the complex [Pt2(CCPh)4(PEt3)2(Bun)2(µ-Li)2

Platinum(II) acetylides of the type trans-[Pt(CCR1)2(PEt3)2](1)(R1= Me, Bun, or Ph) lose one equivalent of PEt3 on treatment with organolithium reagents LiR2(2)(R2= Bun, But, or Ph) in hydrocarbon solvents to give the dinuclear complexes [Pt2(CCR1)4(PEt3)2(R2)2(µ-Li)2](3), containing a PtLi2Pt unit. In the presence of better donors (e.g. Et2O, tetrahydrofuran, or NNN′N′-tetramethylethylenediamine) solvation of lithium breaks this dimeric structure leading to the anions (4) of the type trans-[Pt(CCR1)2(PEt3)R2]–. Reaction of the anion (4d)(R1= Ph, R2= Bun) with a further equivalent of LiR2(R2= Bun) gave Li(CCPh) and another anion, cis-[Pt(CCPh)(PEt3)(Bun)2]–. Multinuclear n.m.r. (1H, 7Li, 13C, 31P, and 195Pt) has been used to characterize the highly reactive compounds in solution. The crystal structure of complex (3d)(R1= Ph, R2= Bun) has been determined, which crystallises in space group P21/n, with a= 14.061(4), b= 18.408(4), c= 19.737(7)A, and Z= 4.

ChemInform Abstract: SOLVENTS EFFECTS ON ELECTROCHEMICAL CHARACTERISTICS OF GRAPHITE FLUORIDE-LITHIUM BATTERIES

Graphitfluoride der Typen (C2F)n und (CF)n werden als Kathodenmaterial in Li-Batterien eingesetzt.

Solvents effects on electrochemical characteristics of graphite fluoride—lithium batteries

A study was made of the electrochemical characteristics of graphite fluoride—lithium batteries in various non-aqueous solvents. Two types of graphite fluorides, (C 2F) n and (CF) n were used as cathode materials. The discharge characteristics of graphite fluorides were better in dimethylsulfoxide, γ-butyrolactone, propylene carbonate and sulfolane in that order. The relation between electrode potential of graphite fluoride and solvation energy of lithium ion with each solvent indicates that solvated lithium ion is intercalated into traphite fluoride layers by the electrode reaction. Both the difference in the overpotentials and in the rates of OCV recovery among these solvents further supports the proposed reaction mechanism.

ChemInform Abstract: TETRAMERIC CUBIC STRUCTURES OF TWO SOLVATED LITHIUM ENOLATES

Chemischer InformationsdienstVolume 13, Issue 14 Physical Organic Chemistry ChemInform Abstract: TETRAMERIC CUBIC STRUCTURES OF TWO SOLVATED LITHIUM ENOLATES R. AMSTUTZ, R. AMSTUTZSearch for more papers by this authorW. B. SCHWEIZER, W. B. SCHWEIZERSearch for more papers by this authorD. SEEBACH, D. SEEBACHSearch for more papers by this authorJ. D. DUNITZ, J. D. DUNITZSearch for more papers by this author R. AMSTUTZ, R. AMSTUTZSearch for more papers by this authorW. B. SCHWEIZER, W. B. SCHWEIZERSearch for more papers by this authorD. SEEBACH, D. SEEBACHSearch for more papers by this authorJ. D. DUNITZ, J. D. DUNITZSearch for more papers by this author First published: April 6, 1982 https://doi.org/10.1002/chin.198214059Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume13, Issue14April 6, 1982 RelatedInformation

ChemInform Abstract: ON THE BEHAVIOR AND REACTIVITY OF SOLUTIONS OF COMPLEX HYDRIDES. XIII. SOLVATED LITHIUM TETRAHYDRIDOBORATE AND SODIUM TETRAHYDRIDOBORATE SOLUBLE IN BENZENE

Chemischer InformationsdienstVolume 7, Issue 16 Organoelement Compounds ChemInform Abstract: ON THE BEHAVIOR AND REACTIVITY OF SOLUTIONS OF COMPLEX HYDRIDES. XIII. SOLVATED LITHIUM TETRAHYDRIDOBORATE AND SODIUM TETRAHYDRIDOBORATE SOLUBLE IN BENZENE O. KRIZ, O. KRIZSearch for more papers by this authorP. SOCHOR, P. SOCHORSearch for more papers by this author O. KRIZ, O. KRIZSearch for more papers by this authorP. SOCHOR, P. SOCHORSearch for more papers by this author First published: April 20, 1976 https://doi.org/10.1002/chin.197616295Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume7, Issue16April 20, 1976 RelatedInformation

Electronic structure and geometry of bis(dimethyl ether)allyllithium

The geometry-optimized structure of bis(dimethyl ether)allyllithium has been calculated by the INDO method. The metalcarbanion interaction involves both σ and π bonding. Approximately 0.82 electrons are transferred from the allyl anion to the solvated lithium moiety upon formation of the lithiumcarbanion bond.