Insertion of 1-t-butylpropyne into singly tucked-in permethyltitanocene. Synthesis, crystal structure of product and transition-state geometry

Pinkas, Jiřı́; Mach, Karel; Kubišta, Jiřı́; Horáček, Michal; Szarka, Katarí­na; Gyepes, Róbert

doi:10.1016/j.molstruc.2018.04.071

Cited by 4 publications

(9 citation statements)

References 11 publications

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“…Additional information, on the above titanium(III) products and by‐products, was further obtained after their conversion to Ti IV products by chlorination with PbCl 2 . In this way, compound 3aa afforded the Ti IV chloride with the conjugated double bond system preserved ( 5aa ) (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…Additional information, on the above titanium(III) products and by-products, was further obtained after their conversion to Ti IV products by chlorination with PbCl 2 . [16][17][18] In this way, compound 3aa afforded the Ti IV chloride with the conjugated double bond system preserved (5aa) (Scheme 5). The analogous chlorination of products 3b/4b and 3c/4c which contained considerable amounts of titanocene hydride products (cf.…”

Section: Hydrogen-induced Rearrangementsmentioning

confidence: 99%

“…The structure of 3aa was further supported by 1 H and 13 C NMR spectra of its diamagnetic Ti IV chloride 5aa obtained by chlorinating 3aa with PbCl 2 in tetrahydrofuran (THF). [16][17][18] The mechanism of the dihydrogen-induced rearrangement is clarified for 2b to 3b conversion by Density Functional Theory (DFT) computations.…”

Section: Introductionmentioning

confidence: 99%

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Molecular Hydrogen‐Induced Carbon Chain Rearrangement in Cyclopentadienyl‐Tethered Titanium(III) Permethyltitanocene Complexes

et al. 2019

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Dihydrogen added at atmospheric pressure and ambient temperature to cyclopentadienyl-tethered titanium(III) permethyltitanocene complexes induced the rearrangement of their tether [-CH 2 -C(Me)=C(R)-Ti], moving the double bond to the lateral position [-CH 2 -C(=CHR)-CH 2 -Ti]. The methyl substituent on the -carbon from the cyclopentadienyl ring is converted to methylene group binding the rearranged tether to titanium. Subsequent hydrogenation of compounds with [a] J. 128Scheme 4. Rearrangement of 2b to 3b and partial hydrogenation of the latter to 4b and rearrangement of 2c followed by hydrogenation to 4c (solvent hexane, room temperature).

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Section: Resultsmentioning

confidence: 99%

Section: Hydrogen-induced Rearrangementsmentioning

confidence: 99%

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Molecular Hydrogen‐Induced Carbon Chain Rearrangement in Cyclopentadienyl‐Tethered Titanium(III) Permethyltitanocene Complexes

et al. 2019

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“…Seit den ersten Tagen der Verwendung der Bezeichnung "tuck(ed)-in" existieren überaus viele Beispiele fürR eaktionen nach diesem Prinzip, die es unmçglich machen, einen soliden Überblick in dieser Arbeit zu erstellen. Ausd iesem Grunde werden nur ausgewählte repräsentative Reaktionen erwähnt, die sich auf die Gruppe-4-Metalle Titan [5] und Zirconium beziehen. [6] Mehrere Beispiele sind von Mach und Mitarbeitern publiziert worden.…”

Section: Beispiele Füra Nschauliche Bezeichnungenunclassified

Anschauliche Bezeichnungen der Chemie von Metallocen‐Komplexen der Gruppe 4

Rosenthal

2020

Angewandte Chemie

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Drei Beispiele fürd ie Verwendung einfacher und anschaulicher Benennungen in der Organometallchemie von Metallocen-Komplexen der Gruppe 4w erden erklärt und diskutiert. Die Bezeichnung "tuck(ed)-in" betrifft das Verhalten des Decamethyltitanocens [(C 5 Me 5) 2 Ti]o der ähnlicher Komplexe,b ei dem eine oder zwei Methylgruppen Titanhydrid-Komplexew ie [(C 5 Me 5)(C 5 Me 4 CH 2)TiH] oder andere Hydridkomplexed urch C-H-Aktivierung bilden. In der "merrygo-round-reaction" wird die Umlagerung von C-Atomen am Titan in Organometallmolekülen beschrieben, bei der eine Rotation von zwei C-Atomen mit einer Rotation der sechsgliedrigen Dihydroindenyl-Einheit am Titan erfolgt. Das dritte Beispiel "migration" oder "tobogganing" betrifft das "sliding" von Titanocen an der Kette eines linearen Polyins durchK oordinierung von einer oder mehreren Dreifachbindungen. In allen diesen Reaktionen wechselt die Koordinationsweise des Metalls am Cp-oder dem Substratliganden, was mit einer intramolekularen Dynamik verbunden ist.

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“…The nature of this bond is σ-Ti–C for 1 since it is d 1 paramagnetic and highly reactive at ambient temperature (Scheme 1). 1–7…”

Section: Introductionmentioning

confidence: 99%

Reactions of permethyltitanocene tucked-in derivatives with carbon dioxide

et al. 2022

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Insertion of 1-t-butylpropyne into singly tucked-in permethyltitanocene. Synthesis, crystal structure of product and transition-state geometry

Cited by 4 publications

References 11 publications

Molecular Hydrogen‐Induced Carbon Chain Rearrangement in Cyclopentadienyl‐Tethered Titanium(III) Permethyltitanocene Complexes

Molecular Hydrogen‐Induced Carbon Chain Rearrangement in Cyclopentadienyl‐Tethered Titanium(III) Permethyltitanocene Complexes

Anschauliche Bezeichnungen der Chemie von Metallocen‐Komplexen der Gruppe 4

Reactions of permethyltitanocene tucked-in derivatives with carbon dioxide

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