Über Metallalkyl- und Aryl-Verbindungen

Corbelin, Siegfried; Lorenzen, Nis Peter; Kopf, Jürgen; Weiß, Erwin

doi:10.1016/0022-328x(91)80130-c

Cited by 40 publications

(64 citation statements)

References 23 publications

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“…(PMDETA)KCPh 3 solvated monomer [14] (thf)[KCHPh 2 ] 2 solvated dimer [13] Na(TMEDA) 2 (thf){Na[C(SiMe 3 ) 3 ] 2 } separated ion pair [17] [(TMEDA)NaCHPh 2 ] 4 solvated tetramer (ring) [12] (PMDETA) 2 [NaCH(SiMe 3 ) 2 ] ϱ chain [15] [KC(SiMe 3 ) 3 ] ϱ chain [18a] [KC(SiMe 3 ) 2 Ph] ϱ chain [19] [(PMDETA)NaCH 2 Ph] ϱ solvated chain [12] [(thf)KCH( Inspection of these results immediately draws attention to the large proportion of these compounds containing silyl-substituted methyl groups. These groups improve stability because of the absence of a β-hydrogen atom, but also through their bulkiness and electronic stabilisation.…”

Section: Alkylmetal Compoundmentioning

confidence: 99%

“…tural information is known for alkylsodium and -potassium compounds with more stabilising modified/functionalised alkyl groups (see Table 1), such as benzyl, [12] diphenylmethyl, [12,13] triphenylmethyl, [14] bis(trimethylsilyl)-methyl, [15,16] tris(trimethylsilyl)methyl, [17,18] and phenylbis-(trimethylsilyl)methyl. [19] Structural motifs which can be found in this group of compounds range from solvated monomers, [14] solvated dimers, [13] separated ion pairs, [17] solvated tetramers, [12,16b] chains, [15,18a,19] and solvated chains.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Structures of [(Trimethylsilyl)methyl]sodium and ‐potassium with Bi‐ and Tridentate N‐Donor Ligands

et al. 2011

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[(Trimethylsilyl)methyl]sodium [NaCH2SiMe3] (1) was prepared by a metathesis reaction of [(trimethylsilyl)methyl]lithium [LiCH2SiMe3] with sodium tert‐butoxide in n‐hexane. Polydentate donors such as N,N,N′,N′‐tetramethylethylenediamine (TMEDA) and N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) form n‐hexane‐soluble complexes of 1 and the potassium congener [KCH2SiMe3] (2). The crystal structures of the polymers [(TMEDA)NaCH2SiMe3] (1a) and [(PMDETA)KCH2SiMe3] (2a) were determined as infinite helical chains exhibiting 31 or 32 screw‐axis symmetry. Compound 2b was obtained as the donor‐deficient heterocubane pseudotetramer [(TMEDA)3(KCH2SiMe3)4], with intermolecular interactions of the TMEDA‐uncoordinated potassium atom with a peripheral methyl group of a neighbouring tetramer to form infinite chains. The relatively easy accessibility and stability should make these (trimethylsilyl)methyl compounds of sodium and potassium valuable starting points for further exploration of the chemistry of these common‐utility heavier alkali metals.

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Section: Alkylmetal Compoundmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis and Structures of [(Trimethylsilyl)methyl]sodium and ‐potassium with Bi‐ and Tridentate N‐Donor Ligands

et al. 2011

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“…The silicon atom is located 0.198(5) A above the Cp ring plane. The Si-C-Ph angle of 114.7(15) ° corresponds to a normal r/~-benzyl ligand [43][44][45][46][47][48].…”

Section: Description Of the Crystal Structure Of [Zr(~l 5-c 5 H4(simementioning

confidence: 99%

Synthesis and reactivity of new silyl substituted monocyclopentadienyl zirconium complexes. X-ray molecular structure of [Zrη5-C5H4 (SiMe2CH2Ph)(CH2Ph)3]

Ciruelo¹,

Cuenca²,

Gómez³

et al. 1997

Journal of Organometallic Chemistry

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New silyl substituted monocyclopentadienyl complexes of Zr(IV) were synthesized from the precursor [Zr{@-CsH4(SiMe2C1)}CI 3] (1). The reaction of 1 with the lithium benzamidinate salt Li[C(Ph){N(SiMe3)} 2] leads to the complex [Zr{r/5-CsHa(SiM%C1)}{C(Ph)[N(SiMe3)]2}C12 ] (2), which decomposes slowly in solution with elimination of SiMe3C1. Complex 1 reacts with alkyl, amido and alkoxo transfer reagents (4 equiv.) to afford complexes [Zr{@-CsH4(SiMe2X)}X 3] (X = NMe 2 (3), OSiMe 3 (4), CH2CMe2Ph (5), C6H 5 (6), C6F 5 (7) and CH2SiMe 3 (8)) in good yields. Compounds 6 and 7 retain diethyl ether used as solvent but decompose as soon as they are desolvated under high vacuum conditions. Reaction of 1 with Mg(CH2Ph) 2 • 2THF (4 equiv.) yields the tetrabenzyl complex [Zr{@-CsHa(SiMe2CH2Ph)}(CH2Ph) 3] (9). The lH and 13C NMR data of the latter compound are discussed in terms of the non-classical coordination mode of the CH 2 Ph ligand, The molecular structure of [Zr{~75-C 5H4(SiMe2CH 2 Ph)}(CH2 Ph)3] 9 has been determined by X-ray diffraction methods. The coordination geometry around the zirconium atom shows a substituted @-cyclopentadienyl ring and three different benzyl ligands: a distorted ~2-benzyl group; a normal r/l-benzyl group; and a benzyl ligand with an intermediate coordination mode. The benzyl fragment bonded to silicon points away from the metal center. 9 crystallized in monoclinic space group P21/c with a = 11.268(3) A, b = 10.846(3) A, c = 27.734(6) A, /3 = 100.29(1) °, V = 3334.9(15) ~3 for Z = 4. The tetraalkylated compounds 6, 7 and 9 are excellent precursors for the preparation of the chloro derivatives. Reactions of these complexes with 3 equiv, of HC1 gave the corresponding trichloro [Zr{@-CsH4(SiMezR)}C13] (R = C6H 5 (10), C6F' 5 (11), CHePh (12)). The monochloro [Zr{@-CsH4(SiM%CH2Ph)}(CH2Ph)2C1] (13) and the dichloro derivative [Zr{@-CsH4(SiMezCHzPh)}(CHzPh)C12] (14) are observed, at 60°C and 90°C, respectively, by NMR experiments in deuterated chloroform. Complexes 10 and 11 also retain coordinated solvent, decomposing slowly when it is removed. 1 and 12 in the presence of MAO as cocatalyst, at 25°C and 1 atm of monomer pressure, cause the polymerization of ethylene with moderate activities, while under similar conditions, polymerization of propylene and styrene proceeds giving only traces of atactic materials. © 1997 Elsevier Science S.A.

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“…The related structures show new coordination patterns in organolithium chemistry. Solid-state structures of [(donor)· MCH 2 Ph] n , M = s-block metal, have been reported [4] and were studied theoretically. [5] Benzyllithium is an important industrial bulk material as, for example, a starting material for drug production and polymerization, but is difficult to produce in the required purity.…”

Section: In Memory Of Gernot Bochementioning

confidence: 99%

Pure α‐Metallated Benzyllithium from a Single‐Crystal‐to‐Single‐Crystal Transition

et al. 2011

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Über Metallalkyl- und Aryl-Verbindungen

Cited by 40 publications

References 23 publications

Synthesis and Structures of [(Trimethylsilyl)methyl]sodium and ‐potassium with Bi‐ and Tridentate N‐Donor Ligands

Synthesis and Structures of [(Trimethylsilyl)methyl]sodium and ‐potassium with Bi‐ and Tridentate N‐Donor Ligands

Synthesis and reactivity of new silyl substituted monocyclopentadienyl zirconium complexes. X-ray molecular structure of [Zrη5-C5H4 (SiMe2CH2Ph)(CH2Ph)3]

Pure α‐Metallated Benzyllithium from a Single‐Crystal‐to‐Single‐Crystal Transition

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