Di(tertiobutylcyclopentadienyl)zircona[1]ferrocenophane precurseur de zirconocenes disubstitués dissymetriquement

Broussier, R.; Rold, A. Da; Gautheron, B.

doi:10.1016/0022-328x(92)83087-x

Cited by 20 publications

(7 citation statements)

References 34 publications

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“…The synthetic procedure involved a low-temperature reaction of dilithioferrocene´n TMEDA with Ph 2 SiCl 2 . [7] In the subsequent 20 years a range of analogous species with Group 14 (Si, Ge) [8] , Group 15 (P, As) [8±10] , and Group 4 (Ti, Zr, Hf) [11,12] bridging elements were isolated. These molecules all possess strained structures with ring tilts between the planes of the cyclopentadienyl ligands (a) of 6 ± 278 and angles between the ipso-C À E bonds and the planes of cyclopentadienyl ligands (b) of 28.8 ± 40.18, and have attracted attention because of their interesting reactivity and their ability to function as surface-derivatization reagents (for example, for silica) as well as their use as ROP monomers.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Reactivity, and Ring-Opening Polymerization (ROP) of Tin-Bridged [1]Ferrocenophanes

et al. 1998

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Abstract:The first examples of tinbridged [1]ferrocenophanes, Fe(h-C 5 H 4 ) 2 -SntBu 2 (7a) and Fe(h-C 5 H 4 ) 2 SnMes 2 (7b) have been synthesized by the low-temperature reaction of Fe(h-C 5 H 4 Li) 2´n TME-DA (TMEDA N,N,N',N'-tetramethylethylenediamine) with tBu 2 SnCl 2 and Mes 2 SnCl 2 (Mes 2,4,6-trimethylphenyl), respectively. They were isolated in 65 % (7a) and 85% (7b) yield as orange crystalline solids, which were characterized by multinuclear NMR and UV/Vis spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray diffraction. The tilt angles between the planes of the cyclopentadienyl rings are 14.1(2)8 for 7a and 15.2(2)8 (average) for the three independent molecules of 7b in the unit cell. Although they have significantly smaller tilt angles than analogous [1]ferrocenophanes with the lighter Group 14 elements silicon or germanium in the bridge, 7 a and 7 b still readily undergo ring-opening polymerization (ROP) by thermal reaction in the solid state (7 a at 150 8C; 7 b at 180 8C), to give highmolecular-weight poly(ferrocenylstannane)s [Fe(h-C 5 H 4 ) 2 SntBu 2 ] n (8 a) and [Fe(h-C 5 H 4 ) 2 SnMes 2 ] n (8 b). Remarkably, 7 a and 7 b were also found to polymerize in solution at room temperature in the absence of externally added initiators. ROP is much more rapid for 7 a than for 7 b in solution. The cyclic dimers [Fe(h-C 5 H 4 ) 2 SnR 2 ] 2 (3; R tBu, Mes) were formed as by-products in amounts which depended on the solvent. Electrochemical studies of the cyclic dimers and polymers indicated the presence of significant Fe´´´Fe interactions that are mediated by the tin-atom spacer. When benzene solutions of 7 a and 7 b were treated with small amounts of Karstedts catalyst, slower polymerization was observed. Stoichiometric reaction of Pt(1,5-cod) 2 (cod cyclooctadiene) with 7 a yielded the novel trimetallic 1-stanna-2-platina[2]ferrocenophane Fe(h-C 5 H 4 ) 2 Pt(1,5-cod)SntBu 2 (9), which functioned as a sluggish catalyst for the ROP of 7 a and 7 b.

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Section: Introductionmentioning

confidence: 99%

Synthesis, Reactivity, and Ring-Opening Polymerization (ROP) of Tin-Bridged [1]Ferrocenophanes

et al. 1998

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“…In this case we again have observed formation of the monosubstituted derivative 2c. Interestingly the synthesis of 2c has only been previously described from the zirconocene precursor [64]. Crystals of 1c suitable for X-ray diffraction study were grown from layered chloroform-hexane.…”

Section: Resultsmentioning

confidence: 99%

Preparation and characterization of new chiral ferrocenyl selenides

Białek

Kowalski

Ścianowski

et al. 2012

Journal of Organometallic Chemistry

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“…Therefore, the substitution of these Cp rings can be designed to increase the solubility of complexes in non-polar solvents without severe effects in the analytical process. Furthermore, substitution of Cp rings with specific substituents can be used to tune the reactivity of the resulting complex towards protic reagents, 22 and thus increase their scope for use as precursors for electronic materials. The use of ferrocene instead of bulky organic linkers to stabilize metallocene chalcogenide moieties both reduces carbon contamination upon decomposition and facilitates delivery of early transition metal, chalcogen and iron elements in one step for potential iron-doped metal diselenide synthesis.…”

Section: Resultsmentioning

confidence: 99%

“…20,21 An important strategy to increase the stability and control the reactivity of metallocene dichalcogenides is the choice of appropriate ligands surrounding the transition metal. 22 Aryl substituents bonded to metallocene dichalcogenides have been shown to increase the molecular stability in comparison with alkyl fragments. 16 Also, the choice of flexible organic groups in the selenolato ligands are shown to allow maximum interaction between the d-orbitals of the metal and the p-orbitals of the chalcogen atoms.…”

Section: Introductionmentioning

confidence: 99%

Macrocycles containing 1,1′-ferrocenyldiselenolato ligands on group 4 metallocenes

et al. 2018

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were prepared and characterized by 77 Se NMR spectroscopy and the crystal structures of 1-3 and 5 were determined by single-crystal X-ray diffraction. The crystal structure of 4 is known and the complex is isomorphous with 5. 1-5 form mutually similar macrocyclic tetranuclear complexes in which the alternating Fe(C 5 H 4 Se) 2 and M(C 5 H 4 R) 2 centers are linked by selenium bridges. The thermogravimetric analysis (TGA) of 1-3 under a helium atmosphere indicated that the complexes undergo a two-step decomposition upon heating. The final products were identified using powder X-ray diffraction as Fe x MSe 2 , indicating their potential as single-source precursors for functional materials.

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Di(tertiobutylcyclopentadienyl)zircona[1]ferrocenophane precurseur de zirconocenes disubstitués dissymetriquement

Cited by 20 publications

References 34 publications

Synthesis, Reactivity, and Ring-Opening Polymerization (ROP) of Tin-Bridged [1]Ferrocenophanes

Synthesis, Reactivity, and Ring-Opening Polymerization (ROP) of Tin-Bridged [1]Ferrocenophanes

Preparation and characterization of new chiral ferrocenyl selenides

Macrocycles containing 1,1′-ferrocenyldiselenolato ligands on group 4 metallocenes

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