Novel acetylene complexes of titanocene and permethyltitanocene without additional ligands. Synthesis spectral characteristics and X-ray diffraction study

Burlakov, Vladimir V.; Polyakov, A. V.; Yanovsky, A.I.; Struchkov, Yu. T.; Shur, V. B.; Vol'pin, M. E.; Rosenthal, Uwe; Görls, Helmar

doi:10.1016/0022-328x(94)87082-9

Cited by 178 publications

(134 citation statements)

References 15 publications

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“…They both demonstrate the characteristically bent metallocene arrangement of ligands around titanium. [22] Distances from the titanium center to the ring centers [4] (1.311 (4) [23] (1.308 (3) ), indicates that the bonding in 4 and 5 should be considered weaker. This can be attributed to the fact that the plane of the metallacyclopropene is explicitly bent in the direction of the coupling Cp* ligand.…”

Section: Resultsmentioning

confidence: 99%

Different C−C Coupling Reactions of Permethyltitanocene and Permethylzirconocene with Disubstituted 1,3-Butadiynes

et al. 2000

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Herein we describe different C-C coupling reactions of permethyltitanocene and -zirconocene with disubstituted 1,3-butadiynes. The outcomes of these reactions vary depending on the metals and the diyne substituents. The reduction of [Cp2*MCl2] (Cp* = C5Me5; M = Ti, Zr) with Mg in the presence of disubstituted butadiynes RC triple bond C-C triple bond CR' is suitable for the synthesis of different C-C coupling products of the diyne and the permethylmetallocenes, and provides a new method for the generation of functionalized pentamethyl-cyclopentadienyl derivatives. For M = Zr and R = R' = tBu, the reaction gives, by a twofold activation of one pentamethylcyclopentadienyl ligand, the complex [Cp*Zr[-C(=C=CHtBu)-CHtBu-CH2-eta5-C5Me3-CH2-]] (3), containing a fulvene ligand that is coupled to the modified substrate (allenic subunit). When using the analogous permethyltitanocene fragment "Cp2*Ti", the reaction depends strongly on the substituents R and R'. The coupling product of the butadiyne with two methyl groups of one of the pentamethylcyclopentadienyl ring systems, [Cp*Ti[eta5-C5Me3-(CH2-CHR-eta2-C2-CHR'-CH2)]], is obtained with R = R' = tBu (4) and R = tBu, R' = SiMe3 (5). In these complexes one pentamethylcyclopentadienyl ligand is annellated to an eight-membered ring with a C-C triple bond, which is coordinated to the titanium center. A different activation of both pentamethylcyclopentadienyl ligands is observed for R = R' = Me, resulting in the complex [[eta5-C5Me4(CH2)-]Ti[-C(=CHMe)-C(=CHMe)-CH2-eta5-C5Me4]] (6), which displays a fulvene as well as a butadienyl-substituted pentamethylcyclopentadienyl ligand. The influence exerted by the size of the metal is illustrated in the reaction of [Cp2*ZrCl2] with MeC triple bond C-C triple bond CMe. Here the five-membered metallacyclocumulene complex [Cp2*Zr(eta4-1,2,3,4-MeC4Me)] (7) is obtained. The reaction paths found for R = R' = Me are identical to those formerly described for R = R' = Ph.

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Section: Resultsmentioning

confidence: 99%

Different C−C Coupling Reactions of Permethyltitanocene and Permethylzirconocene with Disubstituted 1,3-Butadiynes

et al. 2000

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“…Elemental analyses were carried out at the Analytische Laboratorien in Lindlar, Germany. The titanocene complexes [Cp* 2 Ti(g 2 -Me 3 SiC≡CSiMe 3 )] (15) was prepared by literature procedures [24]. The acetylenes were purchased from Aldrich.…”

Section: Methodsmentioning

confidence: 99%

Terminal Alkynes in the Coordination Sphere of Titanocene Complexes - Elementary Steps in Catalytic Dimerizations and Oligomerizations of Alkynes

Beckhaus

Wagner

Burlakov

et al. 1998

Z. anorg. allg. Chem.

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“…[7] Der kleinste Vertreter dieser Gruppe ist das Metallacyclopropen, das formal durch die Addition eines Alkins an ein Metallzentrum gebildet wird. [8] Komplexe monoferrocenylsubstituierter Alkine sind bereits in einigen Metallcarbonylen realisiert und strukturell charakterisiert worden. [9] Außerdem synthetisierten King und Mitarbeiter 1967 den Diferrocenylacetylenkomplex eines Cobaltcarbonyls, dessen Molekülstruktur jedoch nicht durch eine Einkristallrçntgenstrukturanalyse belegt ist.…”

Section: Professor Gerhard Erker Zum 65 Geburtstag Gewidmetunclassified

Ferrocenylsubstituierte Metallacyclen des Titanocens – Oligocyclopentadienylkomplexe mit vielversprechenden Eigenschaften

et al. 2011

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C2 und C4 mit drei Metallocenen: Zwei diferrocenylsubstituierte drei‐ und fünfgliedrige Titanacyclen (siehe Struktur) wurden synthetisiert. Ihre Molekülstruktur im Kristall weist eine symmetrische Anordnung dreier Metallocengruppen auf, die nur durch eine C2‐ bzw. C4‐Kette verbunden sind. Erstmals wurde das elektrochemische Verhalten solcher Systeme untersucht, wobei eine Linearisierung des Liganden im Dikation des Fünfrings beobachtet wurde.

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Novel acetylene complexes of titanocene and permethyltitanocene without additional ligands. Synthesis spectral characteristics and X-ray diffraction study

Cited by 178 publications

References 15 publications

Different C−C Coupling Reactions of Permethyltitanocene and Permethylzirconocene with Disubstituted 1,3-Butadiynes

Different C−C Coupling Reactions of Permethyltitanocene and Permethylzirconocene with Disubstituted 1,3-Butadiynes

Terminal Alkynes in the Coordination Sphere of Titanocene Complexes - Elementary Steps in Catalytic Dimerizations and Oligomerizations of Alkynes

Ferrocenylsubstituierte Metallacyclen des Titanocens – Oligocyclopentadienylkomplexe mit vielversprechenden Eigenschaften

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