Synthese und reaktionen von 4R-1-silacyclohexadien-2,4-eisentricarbonylen

Märkl, Gottfried; Soper, C.J.; Hofmeister, P.; Baier, H.

doi:10.1016/s0022-328x(00)85596-5

Cited by 13 publications

(4 citation statements)

References 13 publications

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“…Thus, it seemed that η 6 -silabenzene complexes might be viable synthetic targets and interesting new examples of π-delocalized silaaromatic ligands. Some support for this notion came from a literature report describing observation of the [η 6 -4-cyclohexyl-1-methylsilabenzene]Fe radical cation in the mass spectrum of [η 5 -4-cyclohexyl-1,1-dimethylsilacyclohexadienyl]Fe(CO) 3 + . Here we report the synthesis and characterization of the first transition metal silabenzene complex and a disilabenzene complex that adopts a metallodisilanorbornadiene structure.…”

Section: Introductionmentioning

confidence: 74%

Silabenzene and Disilabenzene Complexes of Ruthenium

2001

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The syntheses of sila-and disilabenzene complexes of "Cp*Ru" (Cp* ) C 5 Me 5 ) are described. Li[C 5 H 5 SiH( t Bu)] reacted with [Cp*RuCl] 4 to give the neutral silacyclohexadienyl complex Cp*Ru[η 5 -C 5 H 5 SiH( t Bu)] (2), characterized by NMR spectroscopy. Reaction of 2 with the Lewis acid B(C 6 F 5 ) 3 gave the product of Si-H abstraction, [Cp*Ru(η 6 -C 5 H 5 Si t Bu)][BH(C 6 F 5 ) 3 ] (3). Complex 3 represents the first example of an isolated silabenzene complex. The characterization of 3 follows from 1 H, 13 C, 29 Si, 19 F, and 11 B NMR and IR spectroscopies. Finally, trans-1,4-dihydrohexamethyl-1,4-disilacyclohexa-2,5-diene reacted with Cp′(PMe 3 ) 2 -RuCH 2 SiMe 3 (Cp′ ) C 5 Me 4 Et) to give Cp′(PMe 3 )RuH(η 2 -hexamethyl-1,4-disilabenzene) (4), whose structure (by X-ray crystallography) may be described as a metallodisilanorbornadiene.

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Section: Introductionmentioning

confidence: 74%

Silabenzene and Disilabenzene Complexes of Ruthenium

2001

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“…b See ref e. c See ref . d B3LYP/6-311G(d) (C, H, O), 6-311G(3d) (Si), TVZ (17s10p6d)[6s3p3d] (Cr), and TVZ (19s14p9d)[8s6p5d] (Mo)//B3LYP/6-31G(d) (C, H, O, Si) and LANL2DZ (Cr, Mo) …”

Section: Resultsmentioning

confidence: 99%

“…On the other hand, complexation with transition metals is one of the most popular reactions of aromatic compounds, and it may be a useful method for the thermodynamic stabilization of reactive silaaromatic compounds. Märkl and co-workers have reported the observation of an Fe complex of silabenzene, [Fe{4-Cy-(C 5 H 4 SiMe)}] •+ (Cy = cyclohexyl), in the mass spectrum . Tilley and co-workers succeeded in the synthesis of transition-metal complexes with a η 5 -coordinated silolyl anion, which have the conjugated six-π-electron type ligand .…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Properties of η⁶-Silabenzene−M(CO)₃Complexes (M = Cr, Mo)

et al. 2005

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Synthesis of the first neutral η 6 -silabenzene complexes [M(η 6 -C 5 H 5 SiTbt)(CO) 3 ] (M ) Cr (2), Mo (3); Tbt ) 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl) was achieved by the ligand exchange reactions of [M(CH 3 CN) 3 (CO) 3 ] (M ) Cr, Mo) with the kinetically stabilized silabenzene 1. X-ray crystallographic analysis of 2 revealed that the η 6 -coordinated silabenzene rings of the complexes have almost planar geometries with delocalized π-electron structures. The structures of η 6 -silabenzene complexes 2 and 3 were fully characterized by NMR, UV/vis, and IR spectroscopic analysis. All the 1 H, 13 C, and 29 Si NMR chemical shifts of the SiC 5 H 5 rings of 2 and 3 were shifted to upper field relative to those for silabenzene 1, due to the π-coordination of the silabenzene ring to the metal center. The carbonyl stretching frequencies of 2 and 3 were observed in a region of lower wavenumber as compared to those of the corresponding group 6 metal complexes of benzene. In the UV/vis spectra of 2 and 3, the absorption maxima were slightly red-shifted compared to those for the corresponding benzene complexes. The formation of η 6 -silabenzene complexes 2 and 3 is very important from the viewpoints of the novel chemical reactivity of silaaromatics. Silabenzene complexes 2 and 3 were thermally stable under an inert atmosphere but air and moisture sensitive. These compounds underwent ready addition reactions with water exclusively at their 1,2-positions to give the corresponding hydroxysilane 8a. The high regioselectivity observed for the addition reactions to 2 and 3 is in a sharp contrast to the competitive 1,2-and 1,4-addition reactions of free silabenzene 1 with water.

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“…The (metallole -Fe -CH4)+ ion is abundant for 106 and 107 (56 and 59%), but not for 114 (8%).63 These ions are postulated as aromatic fragments, (silabenzene -Fe)+ ions, already invoked in the fragmentation of tricarbonyl(?74-silacyclohexadiene)iron complexes. 103 The possible formation of jj5-metallole species in mass spectrometry has been discussed in section IV.A).…”

Section: Electronic Structuresmentioning

confidence: 99%

Group 14 metalloles. 2. Ionic species and coordination compounds

Colomer,

Corriu,

Lheureux

1990

Chem. Rev.

151

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Synthese und reaktionen von 4R-1-silacyclohexadien-2,4-eisentricarbonylen

Cited by 13 publications

References 13 publications

Silabenzene and Disilabenzene Complexes of Ruthenium

Silabenzene and Disilabenzene Complexes of Ruthenium

Synthesis and Properties of η⁶-Silabenzene−M(CO)₃Complexes (M = Cr, Mo)

Group 14 metalloles. 2. Ionic species and coordination compounds

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Synthese und reaktionen von 4R-1-silacyclohexadien-2,4-eisentricarbonylen

Cited by 13 publications

References 13 publications

Silabenzene and Disilabenzene Complexes of Ruthenium

Silabenzene and Disilabenzene Complexes of Ruthenium

Synthesis and Properties of η6-Silabenzene−M(CO)3Complexes (M = Cr, Mo)

Group 14 metalloles. 2. Ionic species and coordination compounds

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Synthesis and Properties of η⁶-Silabenzene−M(CO)₃Complexes (M = Cr, Mo)