2002
DOI: 10.1002/1521-3749(200205)628:4<755::aid-zaac755>3.0.co;2-i
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Reaktionen von Pentafulven-Komplexen des Titans mit Nitrilen und iso-Nitrilen — Synthese und Isomerisierungen von σ, π-Chelatkomplexen mit Cp∼N-Liganden

Abstract: Inhaltsübersicht. Die Umsetzungen der Fulvenkomplexe Cp* Ti{η 6 ϪC 5 H 4 ϭC(R)(RЈ)}Cl (R ϭ H, RЈ ϭ tBu (1); R ϭ Me, RЈ ϭ iPr (4)) mit Nitrilen und iso-Nitrilen, die zu σ,π-Chelatkomplexen mit CpϳN-Liganden führten, wurden untersucht und die entstehenden Produkte charakterisiert. Während bei der Umsetzung von 1 bzw. 4 mit Nitrilen eine 1,2-Monoinsertion der CN-Einheit in die TiϪC(R)(RЈ) (Fv)-Bindung beobachtet wird, führt die Reaktion mit iso-Nitrilen zur Insertion zweier Moleküle iso-Nitril. Das Ni-Abstract. T… Show more

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Cited by 22 publications
(21 citation statements)
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“…The signals of the C q =CH 2 moiety show characteristic chemical shifts in the 1 H and 13 C NMR spectra at δ 1 H=3.60 and 4.09 ppm and δ 13 C{ 1 H}=81.0 (C q =CH 2 ) and 176.7 ppm (C q =CH 2 ), respectively. The other chemical shifts are in good agreement to titanium enamine complexes reported in the literature …”
Section: Resultssupporting
confidence: 90%
See 2 more Smart Citations
“…The signals of the C q =CH 2 moiety show characteristic chemical shifts in the 1 H and 13 C NMR spectra at δ 1 H=3.60 and 4.09 ppm and δ 13 C{ 1 H}=81.0 (C q =CH 2 ) and 176.7 ppm (C q =CH 2 ), respectively. The other chemical shifts are in good agreement to titanium enamine complexes reported in the literature …”
Section: Resultssupporting
confidence: 90%
“…As expected, the 29 Si{ 1 H} and 31 P{ 1 H} chemical shifts only deviate slightly in relation to complex 2 and free ligands L3 , 4 , which indicates similar chemical environments at the silicon and phosphorus atoms. The 13 C{ 1 H} NMR signals of the C=N moieties at δ 13 C{ 1 H}=195 ppm, like the other NMR data, are typical for complexes derived from insertion reactions of nitriles into the polarized Ti−C q, exo bond of complex 1 …”
Section: Resultsmentioning
confidence: 69%
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“…An insertion of a second nitrile into the ZrH bond would result in an intermediate as shown in Scheme (left). Such a compound has already been isolated in the reaction of 2 with Ph 2 CHCN3 Due to the remaining H atom at the α‐C atom in this case, an H‐shift as a kind of enamine/imine tautomerism17 might occur, leading to the right‐hand structure. Two different reactions are possible for these intermediates influenced by the temperature.…”
Section: Resultsmentioning
confidence: 93%
“…Aditionally, by other reactions the conversion of only one pentafulvene [C 5 H 4 =CR 2 ] 2− to Cp′ ligands [C 5 H 4 −CHR 2 ] 1− was described whereas the other remains as [C 5 H 4 =CR 2 ] 2− ligand. This opens the way to a lot of other synthetically very interesting reactions …”
Section: Examples For Substrate Additionmentioning
confidence: 98%