Synthese und reaktivität von silicium-übergangsmetall-komplexen

Thum, Gerhard; Ries, Wolfgang; Greißinger, Dieter; Malisch, Wolfgang

doi:10.1016/s0022-328x(00)99840-1

Cited by 51 publications

(16 citation statements)

References 11 publications

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“…It has been reported that Cp(CO) 2 FeSiMe 2 NMe 2 can be synthesized through the reaction of Cp(CO) 2 FeSiMe 2 Cl with LiNMe 2 via salt elimination. 11 By applying this method, we attempted the synthesis of a related complex, Cp*(CO) 2 FeSi-Me 2 NEt 2 , in which the bulky and electron-donating Cp* ligand was introduced to stabilize the complex and its derivatives. However, even after heating the reaction mixture at 70 ЊC, the desired product was not formed, and the starting complex was recovered.…”

Section: Reaction Of Cp*(co) 2 Fesime 2 CL With Linetmentioning

confidence: 99%

Reactions of M[(η5-C5Me5)Fe(CO)2] with ClSiMe2NR2 in THF, Et2O and toluene (M = Li and K; R = Me, Et, iPr and Ph)

2003

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Treatment of K[Cp*Fe(CO) 2 ] (Cp* = η 5 -C 5 Me 5 ) with ClSiMe 2 NR 2 (R = Me, Et, i Pr, Ph) in THF afforded Cp*(CO) 2 -Fe(CH 2 ) 4 OSiMe 2 NR 2 accompanied with ring-opening and incorporation of a THF molecule between iron and silicon atoms. On the other hand, reactions between Li[Cp*Fe(CO) 2 ] and ClSiMe 2 NR 2 in diethyl ether (for R = Me, Et), or in toluene in the presence of N,N,NЈ,NЈ-tetramethylethylenediamine (TMEDA) (for R = i Pr, Ph) afforded the corresponding Cp*(CO) 2 FeSiMe 2 NR 2 (R = Me, Et, i Pr, Ph), where the anionic complex was freshly prepared by treatment of Cp*(CO) 2 FeH with n-BuLi. In the case of the reaction of Li[Cp*Fe(CO) 2 ] with ClSiMe 2 NPh 2 , although the formation of the diphenylamino derivative Cp*(CO) 2 FeSiMe 2 NPh 2 was confirmed by NMR spectroscopy, purification of the product was unsuccessful. Subsequently, the exclusive formation of Cp*(CO) 2 FeSiMe 2 NPh 2 was achieved by means of irradiation of Cp*(CO) 2 FeMe and HSiMe 2 NPh 2 in toluene.

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Section: Reaction Of Cp*(co) 2 Fesime 2 CL With Linetmentioning

confidence: 99%

Reactions of M[(η5-C5Me5)Fe(CO)2] with ClSiMe2NR2 in THF, Et2O and toluene (M = Li and K; R = Me, Et, iPr and Ph)

2003

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“…Examples include the syntheses of compounds of the type, L n M-SiR 3 À n X n , where X can be H [1], R [2], OH [3,4], OR [5], SR [6], NR 2 [7], and F [8,2]. Furthermore, several complexes containing the dimethylamino-bridged bis(silylene) ligand system, have been prepared directly from reaction between HSiMe 2 NMe 2 and chlorodimethylsilyl complexes of ruthenium(II) and osmium(II) in complex reactions in which one step may involve a nucleophilic substitution at silicon [9].…”

Section: Introductionmentioning

confidence: 99%

Nucleophilic substitution reactions at the Si–Cl bonds of the dichloro(methyl)silyl ligand in five- and six-coordinate complexes of ruthenium(II) and osmium(II)

Kwok

Lü

Rickard

et al. 2004

Journal of Organometallic Chemistry

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“…If the silicon−germanium bond is transposed into a transition metal environment, changes in the reactivity would be expected. It is now well-established that silicon, germanium, tin, and lead compounds of the type (η 5 -C 5 H 5 )Fe(CO) 2 ER 3 , (E = Si, Ge, Sn, Pb) react with bases such as lithium diisopropylamide (LDA) to effect migrations of the metalloid group from the metal center to the cyclopentadienyl ligand, Scheme …”

Section: Resultsmentioning

confidence: 99%

The Si−Ge Bond: Rearrangements, Migrations, and Cleavages

Sharma

Caballero

et al. 1999

Organometallics

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1-Chloropentamethyl-1-silylgermane, ClSiMe2GeMe3 (1), and 1-chloromethylpentamethyl-1-silylgermane, ClCH2SiMe2GeMe3 (2), undergo Lewis acid-catalyzed rearrangements to ClGeMe2SiMe3 (3) and ClSiMe2CH2GeMe3 (4), respectively. Under similar conditions the isomeric ClGeMe2SiMe3 (3) undergoes a fragmentation reaction involving the formation of Me3SiCl and Me2GeCl2, and ClCH2GeMe2SiMe3 (5) rearranges to ClMe2GeCH2SiMe3 (6). Methyllithium treatment of Ph3SiGeMe3 and Me3SiGePh3 and [1,1‘]-tetramethylsilylgermylferrocenophane [(1,1‘-Me2SiMe2Ge((η5-C5H4)2Fe] results in methylation of the silicon atom and formation of the corresponding germyl anion. When the silicon−germanium-bonded fragment is incorporated into a bimetallic transition metal complex, i.e., (η5-C5H5)Fe(CO)2SiMe2GeMe2Fe(η5-C5H5)(CO)2 (7), base treatment with 1 equiv of lithium diisopropylamide (LDA) leads to predominance of silyl group migration to the cyclopentadienyl ring over germyl migration (9:1). Treatment of 7 with a 2.5 molar excess of LDA, followed by quenching with Me3SnCl, results in migration of both the silyl and germyl ends of the bridging group to form (η5-{Me3Sn(CO)2Fe(η5-C5H4GeMe2SiMe2C5H4})Fe(CO)2SnMe3 (8).

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Synthese und reaktivität von silicium-übergangsmetall-komplexen

Cited by 51 publications

References 11 publications

Reactions of M[(η5-C5Me5)Fe(CO)2] with ClSiMe2NR2 in THF, Et2O and toluene (M = Li and K; R = Me, Et, iPr and Ph)

Reactions of M[(η5-C5Me5)Fe(CO)2] with ClSiMe2NR2 in THF, Et2O and toluene (M = Li and K; R = Me, Et, iPr and Ph)

Nucleophilic substitution reactions at the Si–Cl bonds of the dichloro(methyl)silyl ligand in five- and six-coordinate complexes of ruthenium(II) and osmium(II)

The Si−Ge Bond: Rearrangements, Migrations, and Cleavages

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