Competition among multihapto bonding, solvation, and aggregation. The η1/η2 infinite-chain X-ray structure of indenylsodium · N,N,N′,N′-tetramethyl-1,2-diaminoethane

Schade, Christian; Schleyer, Paul von Ragué; Gregory, Peter S.; Dietrich, Hans; Mahdi, Waruno

doi:10.1016/0022-328x(88)89060-0

Cited by 15 publications

(2 citation statements)

References 104 publications

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“…In this solvent it is likely that all species exist as contact ion pairs in which the Li cation resides preferentially over the anionic ring . This geometry is explicitly shown in X-ray structures of indenyllithium, 1 , 1c, and 3c 1 Comparison of the 1 H NMR, 13 C NMR (in parentheses), and 11 B NMR (in circles) chemical shift values of lithium boratabenzenes, lithium boratanaphthalenes, CpLi, and indenyllithium in THF( d 8 ).…”

Section: Nmr Spectramentioning

confidence: 91%

Synthesis and Properties of 1-Substituted 1-Boratanaphthalenes

Fang

Kampf

1999

Organometallics

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1,4-Dihydro-1,1-dimethyl-1-stannanaphthalene (10) has been prepared by a multistep synthesis starting from α,2-dibromotoluene (6). The reaction of 10 with MeBBr2 followed by LDA afforded lithium 1-methyl-1-boratanaphthalene (2a). The reaction of 10 with BCl3, followed by diisopropylamine and subsequent treatment with LDA, gave lithium N,N-diisopropyl-1-amino-1-boratanaphthalene (2c). The boratanaphthalenes have been characterized using 1H NMR, 11B NMR, and 13C NMR spectroscopy. The pK a of the conjugate acid of 2c is close to that of indene. 2a reacts with [Cp*RuCl]4 to form Ru sandwich compound 4a, in which the boratanaphthalene is η6 bound to Ru. 2c reacts with Cp*ZrCl3 to form a Cp*ZrCl2 adduct 5c, in which the boratanaphthalene unit is unsymmetrically bound to Zr.

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Section: Nmr Spectramentioning

confidence: 91%

Synthesis and Properties of 1-Substituted 1-Boratanaphthalenes

Fang

Kampf

1999

Organometallics

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“…Our initial goals in working with heavy group 2 indenyl complexes were threefold: (1) to develop a unified synthetic approach that would be applicable to the synthesis of indenyl complexes of all three metals and that would obviate the need for metal vapor apparatus or the use of poorly characterized species such as (Ph 3 C)CaI; (2) to prepare indenyl complexes containing substituted indenyl ligands, which should improve the solubility of the compounds in nonpolar solvents; (3) to obtain structural data on the complexes, which would allow us to determine whether the indenyl ligands remain symmetrically (i.e., η 5 ) bound to the metal centers or whether they display evidence for slippage (η 5 → η 3 ). Such data would also add to the limited structural information that is available for main-group indenyl complexes. − We report here our progress toward meeting these goals.…”

Section: Introductionmentioning

confidence: 93%

Synthesis and Crystallographic Study of Indenyl and Isopropylated Indenyl Complexes of Calcium, Strontium, and Barium

Overby

Hanusa

1996

Organometallics

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Reaction of 2 equiv of potassium indenide (KInd) with AeI2 (Ae = Ca, Sr, Ba) in THF produces the bis(indenyl) complexes (Ind)2Ae(thf) n (n = 1 for Sr, Ba; n = 2 for Ca) in high yields. The use of potassium 1,3-diisopropylindenide (KInd2i) with the same diiodides produces the analogous complexes (Ind2i)2Ae(thf) n (n = 1 for Ca; n = 2 for Sr and Ba). All the complexes are air-sensitive solids. Single-crystal X-ray diffraction studies were completed for (Ind)2Ca(thf)2, (Ind2i)2Ca(thf), (Ind2i)2Ba(thf)2, and (Ind)2Sr(thf); these represent the first structurally characterized indenyl complexes of the heavier alkaline-earth metals. The calcium and barium compounds are monomeric, with bent metallocene geometries and average Ae−C distances of 2.73(3), 2.69(2), and 3.03(4) Å for (Ind)2Ca(thf)2, (Ind2i)2Ca(thf), and (Ind2i)2Ba(thf)2, respectively. The strontium complex is an infinite coordination polymer, [(Ind)2Sr(thf)]∞, with both terminal (Sr−C = 2.94 Å (av)) and bridging (Sr−C = 3.07 Å (av)) indenyl ligands. Although the individual Sr−C bond distances differ as much as 0.25 Å, there is no clear indication of slippage toward an η3-configuration. The presence of the two isopropyl substituents on the indenyl ligands makes them effectively as bulky as triisopropylcyclopentadienyl rings.

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Strukturen alkalimetallorganischer und verwandter Verbindungen

Weiß¹

1993

Angew. Chem.

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Die Erforschung der Reaktivitat und Struktur alkalimetallorganischer Verbindungen hat in den letzten Jahrzehnten eine geradezu sturmische Entwicklung durchlaufen. Zu diesen Verbindungen gehoren einige fur das Verstandnis der chemischen Bindung besonders wichtige und auch einfache wie die Methylverbindungen der Alkalimetalle, deren Strukturen nun vollstandig aufgeklart sind. Ganz allgemein erwiesen sich die organischen Verbindungen der Alkalimetalle und auch des Magnesiums als Ionenaggregate, deren Eigenschaften sich durch Solvatisierung, z.B. durch Ether und Amine, stark verandern lassen. Auf diesen Erkenntnissen beruhen auch wichtige Fortschritte bei der Synthese vor allem von Verbindungen der schwereren Alkalimetalle. Lange galten die Alkalimetalle als wenig koordinationsfreundlich, und ihre Komplexchemie bot kaum Uberraschungen. Dieses Bild hat sich vollig gewandelt. Kristallstrukturuntersuchungen erbrachten eine Fulle von oft iiberraschenden Strukturtypen (Ringe, Heterocubane, Ketten, Stapel etc.), nicht nur bei ihren organischen Verbindungen, sondern auch bei ihren Amiden, Imiden, Alkoxiden, Phenoxiden, Enolaten und sogar Halogeniden. Ein Vergleich laat interessante Gemeinsamkeiten der scheinbar so verschiedenen Verbindungen erkennen und fuhrt zu einer allgemeineren Klassifizierung derartiger Strukturtypen mit C-, N-, 0und Halogeno-Liganden. Erwin Weiss. geboren 1926 in ArzberglOberfianken, stiidierte an der Teclinisclien Hocliscliule Miinclien undpromovierte 1956 bei Walter Hieber rnit einer Arbeit ,,Ziir Struktur von Metallcarboii)~herbiridiirigeri irnd Arotiiatenkoniple,~eti". Nacli Aiislaridsaufenthalteii (Massachusetts Institute of Tecltnology, Canibridge, USA, 1956, European-Research-Associates( ERA)-Forscliiirigsitistitirte, Briissel, 1957-1961, iind C)~anamide Eiiropean Research Institute (CERI), Gel$ 1961-1965) erliielt er 1965 einen Ruf an die Universitat Hamburg, an der er bis 1991 lelirte. Ini Mittelpiinkt seiner Forschiingen stehen Syntliese iind Struktiir nietallorganisclier Verbindiingen sowohl von Haiiptgrirppen-als aircli von Neberigrirppeiinietallen. Die vorliegende Ubersiclit entstaiid teihveise walirend eines Forscliutigsai~etitlialts in Paris als nager des franzosischen Alesander-,loti-Hirniboldt-Preises 1992.

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Competition among multihapto bonding, solvation, and aggregation. The η1/η2 infinite-chain X-ray structure of indenylsodium · N,N,N′,N′-tetramethyl-1,2-diaminoethane

Cited by 15 publications

References 104 publications

Synthesis and Properties of 1-Substituted 1-Boratanaphthalenes

Synthesis and Properties of 1-Substituted 1-Boratanaphthalenes

Synthesis and Crystallographic Study of Indenyl and Isopropylated Indenyl Complexes of Calcium, Strontium, and Barium

Strukturen alkalimetallorganischer und verwandter Verbindungen

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