Access a divers dichalcogenophenylenes metallocenes (M = Ti, Zr, Hf). Premier exemple d'un ditellurophenylene-zirconocene

Meunier, Philippe; Gautheron, B.; Mazouz, Ahmed

doi:10.1016/0022-328x(87)85066-0

Cited by 22 publications

(3 citation statements)

References 8 publications

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“…Meunier et al have shown that early metal chalcogenates can be derived from the reaction of metallocene-dialkyls with elemental S, Se, or Te . In attempts to effect similar sulfur insertion into Ti−Me bonds, the reaction of ( t -Bu 3 PN) 2 TiMe 2 13 with S 8 in toluene was performed.…”

Section: Resultsmentioning

confidence: 73%

Synthesis, Structure, and Reactivity of Titanium Phosphinimide Thiolate Complexes

et al. 2002

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A series of titanium-phosphinimide thiolate complexes were prepared employing either thiolate for chloride metathesis or protonolysis of metal-carbon bonds by thiols. In these ways the following species were obtained:Reactions of (t-Bu 3 PN) 2 TiMe 2 with 1 equiv of HSCH 2 Ph gave a cyclometalated species 17, (t-Bu 3 PN) 2 Ti(η 2 -SCHPh). The analogous reaction of 1 equiv of phenylthiol generated the species (t-Bu 3 PN) 2 Ti(Me)(SPh) 18. While 17 and 18 could not be isolated free of 14 and 15, respectively, the analogous reaction of tert-butylthiol afforded (t-Bu 3 PN) 2 Ti(Me)(St-Bu) 19 cleanly. Attempts to effect sulfur insertion into Ti-Me bonds were undertaken via the reaction of (t-Bu 3 PN) 2 TiMe 2 with S 8 but gave instead the species (t-Bu 3 PN) 2 Ti(η 2 -S 5 ) 20. The reactivity of the thiolate derivatives, 3-5 with excess AlMe 3 , was examined. Spectroscopic and crystallographic studies revealed the formation of (CpTi(µ-SR)(µ-NPi-Pr 3 )(C)(AlMe 2 ) 2 -(µ-SR)AlMe (R ) CH 2 Ph 21, Ph 22, t-Bu 23). Analogous reactions of 7 and 8 with AlMe 3 afforded [Cp(i-Pr 3 PN)Ti(SRS)]‚(AlMe 3 ) 3 (R ) (CH 2 ) 3 24, ((CH 2 ) 2 (C 6 H 4 )) 25). The mechanistic implications of the observed multiple C-H bond activation are considered. Crystallographic studies of 4, 6, 7, 14, 16, and 20-23 are reported.

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Section: Resultsmentioning

confidence: 73%

Synthesis, Structure, and Reactivity of Titanium Phosphinimide Thiolate Complexes

et al. 2002

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“…Arnold and co-workers have shown that [Cp 2 Zr{TeC(SiMe 3 ) 3 } 2 ] forms in situ at low temperature (−60 °C) but could not be isolated as it undergoes elimination of Te at around −20 °C in solution . Aryl tellurolates such as [Cp 2 M(TePh) 2 ] and [Cp 2 M( o -C 6 H 4 Te 2 )] (M = Ti, Zr or Hf) and the bulky silyltellurolates [Cp 2 M{TeSi(SiMe 3 ) 3 } 2 ] (M = Ti or Zr) represent the only related tellurolate complexes . Attempts to prepare the corresponding [Cp 2 Ti(TeBu t ) 2 ] using a similar method failed, with addition of the LiTeBu t solution leading to reduction to a dark blue Ti(III) species.…”

Section: Resultsmentioning

confidence: 99%

Evaluation of Group 4 Metal Bis-cyclopentadienyl Complexes with Selenolate and Tellurolate Ligands for CVD of ME₂ Films (E = Se or Te)

et al. 2008

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The selenolate and tellurolate complexes [Cp2M(SeR)2] (M = Ti, Zr, or Hf; R = Me or But) and [Cp2M(TeBut)2] (M = Zr or Hf) have been prepared and characterized by 1H, 13C{1H}, 77Se{1H} and 125Te{1H} NMR spectroscopy and microanalysis. Crystal structures of representative examples are reported, together with the structure of the oxo-bridged species [{Cp2Zr(SeMe)}2(μ-O)] formed by partial hydrolysis. Trends in the NMR parameters are discussed. These molecular [Cp2M(SeBut)2] complexes are shown to be suitable as precursors for the single source LPCVD of intensely colored MSe2 thin films for each of the Group 4 elements, confirmed by SEM/EDX and PXD. These are the first examples of single source CVD of ZrSe2 and HfSe2 thin films. The corresponding [Cp2M(TeBut)2] species (M = Zr or Hf) deposit elemental Te under similar LPCVD conditions.

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“…13,15 Special interest was focussed on zirconocene dichalcogenides although high temperatures were required for the complex formation. 3,[15][16][17] Access to titanium and hafnium analogues through transmetallation decreased their overall yields dramatically to 40%, 18 and therefore the use of dilithium salts of diselenolate ligands with metallocene dichlorides was a good compromise for simple synthetic design and achieving high yields. 19 Few examples are found in the literature involving sulfur and tellurium analogue species.…”

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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Access a divers dichalcogenophenylenes metallocenes (M = Ti, Zr, Hf). Premier exemple d'un ditellurophenylene-zirconocene

Cited by 22 publications

References 8 publications

Synthesis, Structure, and Reactivity of Titanium Phosphinimide Thiolate Complexes

Synthesis, Structure, and Reactivity of Titanium Phosphinimide Thiolate Complexes

Evaluation of Group 4 Metal Bis-cyclopentadienyl Complexes with Selenolate and Tellurolate Ligands for CVD of ME₂ Films (E = Se or Te)

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

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Access a divers dichalcogenophenylenes metallocenes (M = Ti, Zr, Hf). Premier exemple d'un ditellurophenylene-zirconocene

Cited by 22 publications

References 8 publications

Synthesis, Structure, and Reactivity of Titanium Phosphinimide Thiolate Complexes

Synthesis, Structure, and Reactivity of Titanium Phosphinimide Thiolate Complexes

Evaluation of Group 4 Metal Bis-cyclopentadienyl Complexes with Selenolate and Tellurolate Ligands for CVD of ME2 Films (E = Se or Te)

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

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Evaluation of Group 4 Metal Bis-cyclopentadienyl Complexes with Selenolate and Tellurolate Ligands for CVD of ME₂ Films (E = Se or Te)