Synthesis and structure of the Li13 cage [{[OP(μ-NtBu)]2Li2}3(LiCl)6Li(Cl/OnBu)0.5(thf)7], containing a [OP(μ-NtBu)]22− dianion

Chan, Wesley Ting Kwok; Eisler, Dana J.; Garcı́a, Felipe; González-Calera, Silvia; McPartlin, Mary; Morey, J. V.; Mulvey, Robert E.; Singh, Sanjay; Steiner, Alexander; Wright, Dominic S.

doi:10.1039/b800051d

Cited by 10 publications

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References 26 publications

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“…[3,13] Incorporation of LiCl into molecular structures is rather common. In these complexes, the above-mentioned structural principle of stacking and ladder formation of (LiX) n rings (n = 2 or 3) is maintained, as in [Li 8 Cl 7 ] + with two corner-sharing (LiCl) 4 heterocubane cages [14] or in an Li 4 O 3 Cl cubane cage. [15] In Li[{MeAl(PPh) 3 Li 4 (thf) 3 } 4 (m 4 -Cl)] the central chloride anion shows small separations from four lithium atoms, whereas the other twelve lithium atoms coordinate to THF molecules.…”

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confidence: 96%

A Dilithium 1,4‐Butanediide with a Chlorine‐Centered Li₁₂ Icosahedral Structure

Fischer¹,

Görls²,

Westerhausen³

2009

Angew Chem Int Ed

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Dedicated to Professor Dirk Walther on the occasion of his 70th birthdayFirst organolithium compounds were prepared in the middle of the 19th century, [1] and today they continue to play a key role in organometallic chemistry for many reasons such as commercial availability, straightforward preparative procedures, and a broad application spectrum. To understand and tune the properties of organolithium derivatives, their structures have been investigated in the solid state as well as in solution. The structural diversity of organolithium derivatives is a consequence of aggregation often based on triangle-based Li n polyhedrons and platonic bodies. The triangular faces often are capped by carbanions, thus leading to short Li À Li contacts. Small aggregation degrees can be achieved with bulky substituents and by addition of Lewis bases L such as ethers or amines. Depending on the coligand L and on the bulkiness of R, the following structures are the most common: [2] Higher nuclearity and aggregation degrees are rather seldom, and usually similar structural features are observed such as (LiX) 2 and (LiX) 3 rings that dimerize to cubes or hexagonal prisms or aggregate to ladder-like structures. [2][3][4] Whereas in molecular organolithium chemistry larger lithium cages are to date unknown, icosahedral cages that contain an interstitial lithium atom are known for zero-valent lithium. These lithium(0)-centered Li 13 icosahedra were found in intermetallic phases such as Li 18.9 Na 8.3 Ba 15.3 [5] or the subnitride Li 80 Ba 39 N 9 .[6] Interpenetrating lithium icosahedra Li 19 formed during the crystallization of Li 33.3 Ba 13.1 Ca 3[5] and of binary Li 44 Ba 19 .[7] Icosahedra seem to be typical in Li-rich intermetallic compounds. In these lithium(0) clusters, Li À Li separations between 287 and 344 pm were found.These results suggest that icosahedral cages of lithium(I) cations should also be feasible. To overcome electrostatic repulsion between lithium cations, the lithium cage has to contain an anion X nÀ , which is surrounded by the Li + ions (Figure 1). However, the presence of halide ions in many lithium organometallic compounds does not lead to halide-centered lithium cages, but the halide ion is able to replace alkyl groups which cap Li 3 faces of lithium polyhedrons. This substitution leads to less reactive organolithium compounds, for example [Li 4 Me 4Àn X n ] with a central Li 4 tetrahedron.[8] Therefore, the concept had to be expanded, and as an outer organic clamp a 1,w-butanediide ion was used.The reaction of lithium sand with 1,4-dichlorobutane in diethyl ether [9] led to a clear solution which contained several chemically different 1,4-butanediide anions, as determined by 1 H and 13 C NMR spectroscopy. Cooling of the reaction mixture led to the precipitation of single crystals. However, a high-quality structure determination failed owing to heavy disordering of the cation. Nevertheless, the structure determination suggested a solvent-separated ion pair [Li(Et 2 O) 4 ] [Li 12 {m 3 ,m 3 -(CH 2 ) 4 } 6 (@...

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mentioning

confidence: 96%

A Dilithium 1,4‐Butanediide with a Chlorine‐Centered Li₁₂ Icosahedral Structure

Fischer¹,

Görls²,

Westerhausen³

2009

Angew Chem Int Ed

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“…[3,13] Der Einschluss von LiCl in molekulare Strukturen ist dabei recht häufig. Die Strukturen solcher Komplexe folgen dem Prinzip der Anellierung und Stapelung von (LiX) n -Ringen (n = 2 oder 3), wie in [Li 8 Cl 7 ] + mit zwei eckenverknüpften (LiCl) 4 -Heterocubankäfigen [14] oder in einem Li 4 O 3 Cl-Cubankäfig. [15] In Li[{MeAl(PPh) 3 Li 4 (thf) 3 Lithiumatomen auf, während die anderen zwölf Lithiumatome an THF-Moleküle gebunden sind.…”

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Eine Dilithium‐1,4‐butandiid‐Struktur mit einem chlorzentrierten Li₁₂‐Ikosaeder

Fischer¹,

Görls²,

Westerhausen³

2009

Angewandte Chemie

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Professor Dirk Walther zum 70. Geburtstag gewidmetOrganolithiumverbindungen wurden bereits in der Mitte des 19. Jahrhunderts hergestellt.[1] Sie stellen auch heute noch aus vielerlei Gründen eine wichtige Verbindungsklasse dar, insbesondere wegen der kommerziellen Verfügbarkeit, der leichten Herstellung und des breiten Anwendungsspektrums. [2] Metallreichere Käfige und höhere Aggregationsgrade sind selten und weisen üblicherweise ähnliche Strukturmerkmale auf, wobei (LiX) 2 -und (LiX) 3 -Ringe zu Heterocubanen bzw. hexagonalen Prismen dimerisieren oder trimerisieren oder aber Leiterstrukturen bilden. [2][3][4] Während molekulare Organolithiumverbindungen mit größeren Lithiumkäfigen bisher unbekannt sind, kennt man ikosaedrische Lithiumkäfige mit einem zusätzlichen zentralen Lithiumatom bei Feststoffen. Diese Lithium (0)

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Designing the Macrocyclic Dimension in Main Group Chemistry

Niu

Plajer

García‐Rodríguez

et al. 2018

Chemistry A European J

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Outside the confines and well-established domain of organic chemistry, the systematic building of large macromolecular arrangements based on non-carbon elements represents a significant and exciting challenge. Our aim in the past two decades has been to develop robust synthetic methods to construct new types of main group architectures in a methodical way, principles of design that parallel those used in the organic arena. This Concept article addresses the fundamental thermodynamic and kinetic problems involved in the design and synthesis of main group macrocycles and looks to future developments of macromolecules in this area, as well as new applications in coordination chemistry.

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Synthesis and structure of the Li13 cage [{[OP(μ-NtBu)]2Li2}3(LiCl)6Li(Cl/OnBu)0.5(thf)7], containing a [OP(μ-NtBu)]22− dianion

Abstract: The hydrolysis of [ClP(mu-NtBu)]2 with H2O-Et3N in thf, followed by in situ lithiation with nBuLi gives the Li13 cage [[[O-P(mu-NtBu)]2Li2]3(LiCl)6Li(Cl/OnBu)0.5(thf)7], containing a [O-P(mu-NtBu)]2(2-) dianion that is isoelectronic with ligands of the type [(RN)P(mu-NR)]2(2-).

Cited by 10 publications

References 26 publications

A Dilithium 1,4‐Butanediide with a Chlorine‐Centered Li₁₂ Icosahedral Structure

A Dilithium 1,4‐Butanediide with a Chlorine‐Centered Li₁₂ Icosahedral Structure

Eine Dilithium‐1,4‐butandiid‐Struktur mit einem chlorzentrierten Li₁₂‐Ikosaeder

Designing the Macrocyclic Dimension in Main Group Chemistry

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Synthesis and structure of the Li13 cage [{[OP(μ-NtBu)]2Li2}3(LiCl)6Li(Cl/OnBu)0.5(thf)7], containing a [OP(μ-NtBu)]22− dianion

Abstract: The hydrolysis of [ClP(mu-NtBu)]2 with H2O-Et3N in thf, followed by in situ lithiation with nBuLi gives the Li13 cage [[[O-P(mu-NtBu)]2Li2]3(LiCl)6Li(Cl/OnBu)0.5(thf)7], containing a [O-P(mu-NtBu)]2(2-) dianion that is isoelectronic with ligands of the type [(RN)P(mu-NR)]2(2-).

Cited by 10 publications

References 26 publications

A Dilithium 1,4‐Butanediide with a Chlorine‐Centered Li12 Icosahedral Structure

A Dilithium 1,4‐Butanediide with a Chlorine‐Centered Li12 Icosahedral Structure

Eine Dilithium‐1,4‐butandiid‐Struktur mit einem chlorzentrierten Li12‐Ikosaeder

Designing the Macrocyclic Dimension in Main Group Chemistry

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A Dilithium 1,4‐Butanediide with a Chlorine‐Centered Li₁₂ Icosahedral Structure

A Dilithium 1,4‐Butanediide with a Chlorine‐Centered Li₁₂ Icosahedral Structure

Eine Dilithium‐1,4‐butandiid‐Struktur mit einem chlorzentrierten Li₁₂‐Ikosaeder