Synthese von 1-(but-3-enyl)-2,3,4,5-tetramethylcyclopentadienyl-komplexen des eisens und cobalts

Okuda, Jun; Zimmermann, Karl-Heinz

doi:10.1016/0022-328x(88)80219-5

Cited by 35 publications

(13 citation statements)

References 8 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Reactions of the fulvene complex (g 6 -C 5 Me 4 CH 2 )(C 6 F 5 )Re(CO) 2 Addition of a small excess of potassium diphenylphosphide to a solution of the fulvene precursor produced the anionic complex [(h 5 -C 5 Me 4 CH 2 PPh 2 )Re(C 6 F 5 )(CO) 2 ] -(1) (Scheme 1). The anion 1 was not isolated and it was identified only by IR spectroscopy in solution.…”

Section: Resultsmentioning

confidence: 99%

“…Crystal data and structure refinement for (h 5 :h 1 -C 5 Me 4 CH 2 PPh 2 )Re(CO)2 (3) and (h 5 :h1 -C 5 Me 4 CH 2 PPh 2 )Re(I) 2 CO (6a) ≤ 12, -13 ≤ k ≤ 27, -13 ≤ l ≤ 13 -19 <= h <= 19, -11 <= k <= 11, -22 <= l <= 23 R1 = 0.0221, wR2 = 0.0521 R1 = 0.0561, wR2 = 0.1088 R indices (all data) R1 = 0.0271, wR2 = 0.0534 R1 = 0.088, wR2 = 0.119 Largest difference peak and hole (e A ˚-3 ) 0.314 and -0.910 1.690 and -1.097 was added KI (30 mg, 0.181 mmol) and Me 3 NO•2H 2 O (11 mg, 0.135 mmol). The reaction mixture was stirred at room temperature for 1 h. After this time, the IR spectrum showed the disappearance of the starting complex and one new absorption band at 1885 cm -1 .…”

mentioning

confidence: 99%

See 1 more Smart Citation

Synthesis, reactivity and molecular structure of phosphino tetramethyl cyclopentadienyl complex (η5: η1-C5Me4CH2PPh2)Re(CO)2

et al. 2009

View full text Add to dashboard Cite

The fulvene complex (eta(6)-C(5)Me(4)CH(2))Re(C(6)F(5))(CO)(2) reacts at the exocyclic methylene carbon with potassium diphenylphosphide to yield the anionic species [(eta(5)-C(5)Me(4)CH(2)PPh(2))Re(C(6)F(5))(CO)(2)](-) (). Protonation of with HCl at 0 degrees C produces the hydride complex trans-(eta(5)-C(5)Me(4)CH(2)PPh(2))Re(C(6)F(5))(H)(CO)(2) (). Thermolysis of a hexanes solution of , under nitrogen atmosphere, produces the chelated complex (eta(5):eta(1)-C(5)Me(4)CH(2)PPh(2))Re(CO)(2) () in good yield. The thermolysis under a CO atmosphere affords a mixture of the complexes (eta(5):eta(1)-C(5)Me(4)CH(2)PPh(2))Re(CO)(2) () and (eta(5)-C(5)Me(4)CH(2)PPh(2))Re(CO)(3) (). The reaction of with two electron donor ligands yields (eta(5)-C(5)Me(4)CH(2)PPh(2))Re(CO)(2)(L) (, L = CO; , L = PMe(3); , L = (t)BuNC). Complex also reacts with I(2), HBF(4) and MeOTf to yield the cationic compounds trans-[(eta(5):eta(1)-C(5)Me(4)CH(2)PPh(2))Re(R)(CO)(2)](+) (, R = I; , R = H; , R = Me). Upon treatment with chloroform, the hydride complex converts to the corresponding chloro derivative . The trans stereochemistry for complexes have been assigned on basis of nu(CO) IR intensities and (13)C-NMR chemical shifts. The reaction of the cationic complexes (, ) with KI and Me(3)NO.2H(2)O yields the neutral species cis-(eta(5):eta(1)-C(5)Me(4)CH(2)PPh(2))Re(I)(R)(CO) (, R = I, , R = Me). The molecular structure of and have been determined by X-ray crystallography.

show abstract

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

Synthesis, reactivity and molecular structure of phosphino tetramethyl cyclopentadienyl complex (η5: η1-C5Me4CH2PPh2)Re(CO)2

et al. 2009

View full text Add to dashboard Cite

show abstract

“…Compound 1 was prepared using a procedure similar to that reported by Okuda for C 5 Me 4 (H)CH 2 CH 2 CH CH 2 and was isolated as a golden-yellow liquid in good yield. Its 1 H-NMR spectrum is consistent with a mixture of several isomers, and follows the pattern found for C 5 Me 4 (H)CH 2 CH 2 NMe 2 …”

Section: Resultsmentioning

confidence: 99%

[1-(2-Phenylethyl)-2,3,4,5-tetramethylcyclopentadienyl]- titanium Compounds. Synthesis and Their Use for the Syndiospecific Polymerization of Styrene

et al. 1996

View full text Add to dashboard Cite

A series of monocyclopentadienyltitanium complexes containing the 1-(2-phenylethyl)-2,3,4,5-tetramethylcyclopentadienyl ligand (C5Me4CH2CH2Ph) have been synthesized and characterized. The reaction of C5Me4(SiMe3)CH2CH2Ph (2) with TiCl4 was used to synthesized the trichloro complex (C5Me4CH2CH2Ph)TiCl3 (3), the molecular structure of which was confirmed by an X-ray diffraction study. Compound 3 was further converted into (C5Me4CH2CH2Ph)TiMe3 (4). Reaction of the latter with 1 equiv of [Ph3C][B(C6F5)4] was almost quantitative to give the “cationic” compound [(C5Me4CH2CH2Ph)TiMe2]+[B(C6F5)4]- (5). Complex 5 was thermally unstable in solution and very moisture sensitive. Compound 4 was readily hydrolyzed to [(C5Me4CH2CH2Ph)TiMe2]2(μ-O) (6) upon recrystallization in wet pentane. Structural data indicate intramolecular coordination of the phenyl group to titanium in compound 5, whereas there are no such indications for 3, 4, or 6. The catalytic performance for styrene polymerization of 3 activated with methylaluminoxane (MAO) has been compared with the nonsubstituted reference compound (C5Me5)TiCl3 (7). Complex 5, prepared in situ by reacting 4 with [Ph3C][B(C6F5)4], has also been found to be active for the syndiospecific polymerization of styrene. The polymerization data for 3 and 5 lead to the tentative suggestion that the active species is in equilibrium between two states, one with and one without intramolecular phenyl coordination to Ti. These findings would be consistent with postulated multihapto coordination of styrene by both the vinylic double bond and the aromatic ring to the metal center during the catalytic process.

show abstract

“…[2] They may compete for free coordination sites at the cationic polymerisation centre [3] and can also be used for immobilisation of the catalyst by copolymerisation with the formed polymer or by grafting onto a suitable polymer. [6] Bis[(1-alkylethenyl)cyclopentadienyl]zirconium dichlorides were also used for the syn-thesis of cyclobutane-bridged ansa-metallocene complexes by a photo-induced [22] cycloaddition. However, fully substituted (3-butenyl)tetramethylcyclopentadienyl ligands, although decreasing the Lewis acidity of the metal atom due to electron-donating effect of its hydrocarbyl groups, showed an ability to interact with transition metals by both carbon ± carbon double bonds and cyclopentadienyl ligands.…”

Section: Introductionmentioning

confidence: 99%

Reduction of Bis[η5-(ω-alkenyl)tetramethylcyclopentadienyl]titanium Dichlorides: An Efficient Synthesis of Long-Chainansa-Bridged Titanocene Dichlorides by Acidolysis of Cyclopentadienyl-Ring- Tethered Titanacyclopentanes

Horáček¹,

Štěpnička²,

Gyepes³

et al. 2000

Chem. Eur. J.

View full text Add to dashboard Cite

The reduction of symmetric, fully-substituted titanocene dichlorides bearing two pendant omega-alkenyl groups, [TiCl2(eta5-C5Me4R)2], R = CH(Me)CH= CH2 (1a). (CH2)2CH=CH2 (1b) and (CH2)3CH=CH2 (1c), by magnesium in tetrahydrofuran affords bis(cyclopentadienyl)titanacyclopentanes [Ti(IV)[eta1:eta1: eta5:eta5-C5Me4CH(Me)CH(Ti)CH2CH(CH2(Ti))CH(Me)C5Me4]] (2a), [Ti(IV)[eta1:eta1:eta5: eta5-C5Me4(CH2)2CH(Ti)(CH2)2CH(Ti)(CH2)2C5Me4]] (2b) and [Ti(IV)[eta1:eta1:eta5:eta5-C5Me4(CH2)2CH(Ti)CH(Me)CH(Me)CH(Ti)(CH2)2C5Me4]](2c), respectively, as the products of oxidative coupling of the double bonds across a titanocene intermediate. For the case of complex 1c, a product of a double bond isomerisation is obtained owing to a preferred formation of five-membered titanacycles. The reaction of the titanacyclopentanes with PbCl2 recovers starting materials 1a from 2a and 1b from 2b, but complex 2c affords, under the same conditions, an isomer of 1c with a shifted carbon - carbon double bond, [TiCl[eta5-C5Me4(CH2CH2CH=CHMe)]2] (1c'). The titanacycles 2a-c can be opened by HCl to give ansa-titanocene dichlorides ansa-[[eta5:eta5-C5Me4CH(Me)CH2CH2CH(Me)CH(Me)C5Me4]TiCl2] (3a), ansa-[[eta5:eta5-C5Me4(CH2)8C5Me4]TiCl2] (3b), along with a minor product ansa-[[eta5:eta5-C5Me4CH2CH=CH(CH2)5C5Me4]TiCl2] (3b'), and ansa-[[eta5:eta5-CsMe4(CH2)3CH(Me)CH(Me)CH=CHCH2C5Me4]TiCl2] (3c), respectively, with the bridging aliphatic chain consisting of five (3a) and eight (3b, 3b' and 3c) carbon atoms. The course of the acidolysis changes with the nature of the pendant group; while the cyclopentadienyl ring-linking carbon chains in 3a and 3b are fully saturated, compounds 3c and 3b' contain one asymetrically placed carbon-carbon double bond, which evidently arises from the beta-hydrogen elimination that follows the HCl addition.

show abstract

Synthese von 1-(but-3-enyl)-2,3,4,5-tetramethylcyclopentadienyl-komplexen des eisens und cobalts

Cited by 35 publications

References 8 publications

Synthesis, reactivity and molecular structure of phosphino tetramethyl cyclopentadienyl complex (η5: η1-C5Me4CH2PPh2)Re(CO)2

Synthesis, reactivity and molecular structure of phosphino tetramethyl cyclopentadienyl complex (η5: η1-C5Me4CH2PPh2)Re(CO)2

[1-(2-Phenylethyl)-2,3,4,5-tetramethylcyclopentadienyl]- titanium Compounds. Synthesis and Their Use for the Syndiospecific Polymerization of Styrene

Reduction of Bis[η5-(ω-alkenyl)tetramethylcyclopentadienyl]titanium Dichlorides: An Efficient Synthesis of Long-Chainansa-Bridged Titanocene Dichlorides by Acidolysis of Cyclopentadienyl-Ring- Tethered Titanacyclopentanes

Contact Info

Product

Resources

About