Transition metal compounds containing alkynylsilyl groups − complexes with a metal-silicon bond

Hoffmann, Florian; Wagler, Jörg; Böhme, Uwe; Roewer, Gerhard

doi:10.1016/j.jorganchem.2012.01.019

Cited by 11 publications

(14 citation statements)

References 107 publications

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“…When the lithium salt was added to the titanium tetrachloride, yields were low and erratic. 1 H, 13 C [attached-proton test (APT)], and 29 Si NMR spectra, which are consistent with the molecular structure of 2 and literature data, verify the identity of the compound. Adding the starting materials in the inverse order resulted in a 64 % yield of 2 but only after a workup that included the addition of carbon tetrachloride for the reoxidation [13] of lowvalent titanium species, and that afforded the product as an [12] impure viscous oil.…”

Section: Titanium Compoundssupporting

confidence: 85%

“…Cooling of the mother liquor to -78°C yielded an additional precipitate (yield: 350 mg, 34 %). 1 To this solution was added methanol (500 μL, 396 mg, 12.3 mmol) and then chlorotrimethylsilane (300 μL, 257 mg, 2.37 mmol) at room temperature with stirring and exclusion of light. The final product was very pure, and Mn 2 (CO) 10 could not be detected by 55 Mn NMR spectroscopy.…”

Section: Methodsmentioning

confidence: 99%

“…1 The prepared thallium compound was stirred with Mn(CO) 5 Cl (465 mg, 2.02 mmol) in benzene (20 mL) at room temperature, and a weak gas evolution commenced. The lithium salt immediately dissolved.…”

Section: (B) Synthesis Via Thallium [Dimethyl(phenylethynyl)silyl]cycmentioning

confidence: 99%

“…[1] An alternative approach towards alkynylsilyl-functionalized complexes, which circumvents the sensitivity issues associated with the direct metal-silicon bond, is the insertion of a cyclopentadienyl spacer unit between the metal and the silicon atom, that is, the synthesis of (alkynylsilyl)cyclopentadienyl complexes. [1] An alternative approach towards alkynylsilyl-functionalized complexes, which circumvents the sensitivity issues associated with the direct metal-silicon bond, is the insertion of a cyclopentadienyl spacer unit between the metal and the silicon atom, that is, the synthesis of (alkynylsilyl)cyclopentadienyl complexes.…”

Section: Introductionmentioning

confidence: 99%

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Transition‐Metal Compounds Containing Alkynylsilyl Groups – Cyclopentadienyl Complexes

2012

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6018 was also successful. In contrast, the direct complexation of (alkynylsilyl)cyclopentadiene or the direct alkynylsilylation of cymantrene were not feasible. Redox reactions and the desilylation of the cyclopentadienyl ring were hampering side reactions in all routes but to varying extent. All three complexes were characterized by NMR spectroscopy. 1 and 3 were also studied by IR and UV/Vis spectroscopy. The molecular and crystal structure of compound 1 was determined by X-ray diffraction analysis.metathesis of an (alkynylsilyl)cyclopentadienide], [4] and one of manganese [prepared by the reaction of a (chlorosilyl)cyclopentadienyl complex with a lithium acetylide] [5] reported, which bear alkynylsilyl groups, whereas the corresponding oligosilyl compounds are completely unknown. However, there is a number of related (alkenyl-or allenylsilyl)cyclopentadienyl complexes. [6] Herein, we present a comparative assessment of synthetic routes leading to (alkynylsilyl)cyclopentadienyl complexes, as well as two new examples of such compounds. [7] Scheme 1. Synthesis of compounds 1 and 2.

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Section: Titanium Compoundssupporting

confidence: 85%

Section: Methodsmentioning

confidence: 99%

Section: (B) Synthesis Via Thallium [Dimethyl(phenylethynyl)silyl]cycmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Transition‐Metal Compounds Containing Alkynylsilyl Groups – Cyclopentadienyl Complexes

2012

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“…The formation of 1 suggests an oxidative addition of the hydrosilane to [Rh(PPh 3 ) 3 Cl]. This type of silyl‐hydrido‐Rh III complexes synthetized by Si–H activation of a hydrosilane to a rhodium center are well known . Compound 1 could be synthesized in a good yield by the reaction of Wilkinson's catalyst with an equimolar amount of the tridentate proligand SiMeH( o ‐C 6 H 4 SMe) 2 ( L1 ) in CH 2 Cl 2 at room temperature (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Dehydrogenative Coupling of a Tertiary Silane Using Wilkinson's Catalyst

et al. 2016

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Wilkinson's catalyst [Rh(PPh3)3Cl] results active in the dehydrogenative coupling of the tertiary silane SiMeH(o‐C6H4SMe)2 (L1) to give (o‐C6H4SMe)2MeSi–SiMe(o‐C6H4SMe)2 (L2). The stoichiometric reaction of [Rh(PPh3)3Cl] with L1 affords a new silyl‐hydrido‐RhIII complex [Rh(H){SiMe(o‐C6H4SMe)2}Cl(PPh3)] (1), which results also active in the dehydrocoupling of L1. The unsaturated RhIII compound [Rh(H){SiMe(o‐C6H4SMe)2}(PPh3)][BArF4] (2) was synthesized by reaction of 1 with NaBArF4 and shows lower catalytic activity in this process. Compound 2 reacts with a second equivalent of L1 to form [Rh{SiMe(o‐C6H4SMe)2}2][BArF4] (3), which is inactive in catalysis. Our results allow proposing 1 as an active species in the catalytic reaction and suggesting the formation of 3 as a deactivation process when the unsaturated compound 2 is used as catalyst.

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Synthesis, structural characterization and reactivity towards methanol of a bis(silyl)platinum(II) complex bearing a chelating depe ligand

Zeng

Guo

Sun

et al. 2016

Inorganica Chimica Acta

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Transition metal compounds containing alkynylsilyl groups − complexes with a metal-silicon bond

Cited by 11 publications

References 107 publications

Transition‐Metal Compounds Containing Alkynylsilyl Groups – Cyclopentadienyl Complexes

Transition‐Metal Compounds Containing Alkynylsilyl Groups – Cyclopentadienyl Complexes

Dehydrogenative Coupling of a Tertiary Silane Using Wilkinson's Catalyst

Synthesis, structural characterization and reactivity towards methanol of a bis(silyl)platinum(II) complex bearing a chelating depe ligand

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