Carbon versus Silicon Bridges. Synthesis of a New Versatile Ligand and Its Applications in Organolanthanide Chemistry

Wang, Shaowu; Yang, Qingchuan; Mak, and Thomas C. W.; Xie, Zuowei

doi:10.1021/om990648o

Cited by 62 publications

(60 citation statements)

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“…Each of the two Sm atoms on the common edge coordinates to two µ 4 -O atoms, four triply bridging µ 3 -Cl atoms, and two doubly bridging µ 2 -Cl atoms. Each of the other four Sm atoms is η 5 -bound to one tetramethylcyclopentadienyl ring and σ-bound to one µ 4 -O atom and coordinates to either three triply bridging µ 3 -Cl atoms and one doubly bridging µ 2 -Cl atom or three doubly bridging µ 2 -Cl atoms and one triply [η 5 -Me 2 Si(C 5 Me 4 )(C 2 B 10 H 11 )]NdCl 3 Li(THF) 3 (3) could further react with another 1 equiv of 1 in THF at room temperature to afford, after recrystallization from an ether solution, the bis-ligated compound [η 5 -Me 2 Si(C 5 -Me 4 )(C 2 B 10 H 11 )] 2 Nd(µ-Cl) 2 Li(OEt 2 )(THF) (6). This compound could also be prepared by treatment of NdCl 3 with 2 equiv of 1 in THF at room temperature.…”

Section: Resultsmentioning

confidence: 99%

“…13 C NMR (pyridine-d5): δ 117.2, 114. 6,96.7 (C5Me4),82.6,77.5 (C2B10H10),68.0,25.7 (THF), 15.1, 11.9 (CH3), 3.9 (Si(CH3)2). 11 B NMR (pyridine-d5): δ -3.45 (4), -7.86 (6).…”

Section: Preparation Of [{[(µ-η 5 ):σ-Me2si(c5me4)(c2b10h10)]li-(thf)mentioning

confidence: 99%

“…6,96.7 (C5Me4),82.6,77.5 (C2B10H10),68.0,25.7 (THF), 15.1, 11.9 (CH3), 3.9 (Si(CH3)2). 11 B NMR (pyridine-d5): δ -3.45 (4), -7.86 (6). IR (KBr, cm -1 ): ν 2963 (s), 2882 (s), 2532 (vs), 1453 (m), 1260 (s), 1040 (s), 888 (s), 800 (s).…”

Section: Preparation Of [{[(µ-η 5 ):σ-Me2si(c5me4)(c2b10h10)]li-(thf)mentioning

confidence: 99%

“…Recrystallization from a THF/Et2O solution gave 3 as blue microcrystals (0.318 g, 80%). Preparation of [η 5 -Me2Si(C5Me4)(C2B10H11)]2Nd(µ-Cl)2Li-(OEt2)(THF) (6). To a suspension of NdCl3 (0.125 g, 0.50 mmol) in 15 mL of THF was slowly added a THF solution (10 mL) of [Me2Si(C5Me4)(C2B10H11)]Li(OEt2)0.5 (1; 0.366 g, 1.0 mmol), and the mixture was stirred overnight at room temperature.…”

Section: Preparation Of [{[(µ-η 5 ):σ-Me2si(c5me4)(c2b10h10)]li-(thf)mentioning

confidence: 99%

See 3 more Smart Citations

Tetramethylcyclopentadienyl vs Cyclopentadienyl Substituents. Synthesis and Structural Characterization of Organolanthanide Compounds Derived from the Versatile Ligand Me₂Si(C₅Me₄H)(C₂B₁₀H₁₁)

Yang

Mak

et al. 2001

Organometallics

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Reaction of Me 2 Si(C 5 Me 4 H)Cl with 1 equiv of Li 2 C 2 B 10 H 10 in toluene/Et 2 O gave the monoanionic salt [Me 2 Si(C 5 Me 4 )(C 2 B 10 H 11 )]Li(OEt 2 ) 0.5 (1), which could be conveniently converted into the dianionic salt [{[(µ-η 5 ):σ-Me 2 Si(C 5 Me 4 )(C 2 B 10 H 10 )]Li(THF)} 2 Li][Li(THF) 4 ]‚ THF (2) by treatment with 1 equiv of n-BuLi. 1 reacted with 1 equiv of LnCl 3 in THF to give [η 5 -Me 2 Si(C 5 Me 4 )(C 2 B 10 H 11 )]LnCl 3 Li(THF) 3 (Ln ) Nd (3), Sm (4)). 3 could further react with 1 equiv of 1 to afford [η 5 -Me 2 Si(C 5 Me 4 )(C 2 B 10 H 11 )] 2 Nd(µ-Cl) 2 Li(OEt 2 )(THF) ( 6), which could also be prepared from the reaction of NdCl 3 with 2 equiv of 1. Partial hydrolysis of 4 resulted in the isolation of the novel cluster [{[η 5 -Me 2 Si(C 5 Me 4 )(C 2 B 10 H 11 )]Sm} 2 (µ 2 -Cl) 3 (µ 3 -Cl) 4 Li(OEt 2 ) 2 -Li(THF) 2 Sm(µ 4 -O)] 2 (5). Treatment of 1 with 4 equiv of NaNH 2 in THF, followed by reaction with 1 equiv of YbCl 3 , produced (η 5 -C 5 Me 4 H) 2 Yb(µ-Cl) 2 Li(THF) 2 ( 7). An equimolar reaction between 2 and NdCl 3 yielded the anionic compound [{η 5 : σ-Me 2 Si(C 5 Me 4 )(C 2 B 10 H 10 )} 2 Nd]-[Li(DME) 3 ] (11). Interaction of LnCl 3 with 0.5 equiv of 2 resulted in the isolation of the lanthanocene chloride compounds [{η 10)). Reaction of 9 with 2 equiv of NaN(SiMe 3 ) 2 gave the unsolvated compound [η 5 : σ-Me 2 Si(C 5 Me 4 )(C 2 B 10 H 10 )]YN(SiMe 3 ) 2 (12). Treatment of LnI 2 with 0.5 equiv of 2 afforded the ionic organolanthanide(II) compounds [{η 5 : σ-Me 2 Si(C 5 Me 4 )(C 2 B 10 H 10 )}LnI 2 ][Li(DME) 3 ] 2 (Ln ) Sm (13), Yb ( 14)). All of these new compounds were characterized by various spectroscopic data and element analyses. The solidstate structures of compounds 2, 5-7, 10, and 14 were further confirmed by single-crystal X-ray analyses.

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Section: Resultsmentioning

confidence: 99%

“…13 C NMR (pyridine-d5): δ 117.2, 114. 6,96.7 (C5Me4),82.6,77.5 (C2B10H10),68.0,25.7 (THF), 15.1, 11.9 (CH3), 3.9 (Si(CH3)2). 11 B NMR (pyridine-d5): δ -3.45 (4), -7.86 (6).…”

Section: Preparation Of [{[(µ-η 5 ):σ-Me2si(c5me4)(c2b10h10)]li-(thf)mentioning

confidence: 99%

Section: Preparation Of [{[(µ-η 5 ):σ-Me2si(c5me4)(c2b10h10)]li-(thf)mentioning

confidence: 99%

Section: Preparation Of [{[(µ-η 5 ):σ-Me2si(c5me4)(c2b10h10)]li-(thf)mentioning

confidence: 99%

See 2 more Smart Citations

Tetramethylcyclopentadienyl vs Cyclopentadienyl Substituents. Synthesis and Structural Characterization of Organolanthanide Compounds Derived from the Versatile Ligand Me₂Si(C₅Me₄H)(C₂B₁₀H₁₁)

Yang

Mak

et al. 2001

Organometallics

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“…Various olefin polymerization catalysts have been prepared from fulvenes such as 6,6-dimethylfulvene or 6,6-pentamethylenefu1vene [1][2][3][4]. Furthermore, fulvenes are also fascinating organic ligands in view of their different coordination modes toward transition metals because they have an exocyclic double bond and two endocyclic double bonds.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and crystal structures of cyclopentadienyl dimolybdenum carbonyl complexes

Tian

Han

et al. 2010

Transition Met Chem

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Reactions of the fulvenes C 5 H 4 C(R 1 R 2 ) [(R 1 = CH 2 CH 3 , R 2 = CH 3 (1); R 1 = R 2 = C 2 H 5 (2); R 1 , R 2 = (CH 2 ) 4 (3), R 1 ,R 2 = (CH 2 ) 5 (4)] with Mo(CO) 6 in refluxing xylene gave the corresponding cyclopentadienyl dimolybdenum carbonyl complexes [(g 5 - (7); R 1 0 , R 2 0 = CH(CH 2 ) 4 (8)], which were characterized by elemental analysis, IR and 1 H NMR spectra. The molecular structures were determined by singlecrystal X-ray diffraction. The results indicated the exocyclic double bond of the ligands 1 and 2 changed into a single bond and the exocyclic double bond of the ligands 3 and 4 underwent a double-bond isomerization process.

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Scandium, Yttrium & The Lanthanides: Organometallic ChemistryBased in part on the article Scandium, Yttrium & The Lanthanides: Organometallic Chemistry by R. D. Köhn, G. Kociok‐Köhn, & H. Schumann which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Schumann

Fedushkin

2005

Encyclopedia of Inorganic Chemistry

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The group 3 metals scandium and yttrium and the 4f elements lanthanum to lutetium build up a big variety of organometallic compounds, in general with the metal in the oxidation state +3. Most of them are sandwich complexes Cp 3 Ln, Cp 2 LnX, and CpLnX 2 containing unsubstituted or substituted cyclopentadienyl ligands. In addition, cyclopentadienyl‐free organo rare earth compounds, like alkyl or aryl derivatives, alkenyl, allyl, alkynyl, hydrido, and carbene complexes, and organolanthanide compounds with indenyl, fluorenyl, cyclooctatetraenyl, or with heterocyclic ligands are described. Samarium, europium, and ytterbium form reasonable stable organic compounds in the oxidation state +2, whereas only a few rare earth organometallics with the metal in the oxidation state 0, +1, and +4 are known. All organo rare earth complexes are extremely sensitive to oxygen and water. The development of various synthetic methods as well as intensive single‐crystal X‐ray structure investigations made these highly reactive organometallic compounds available for use as organic synthons, efficient catalysts for polymerization, hydrogenation, hydroamination, and hydrosilylation as well as precursors for Metal Organic Chemical Vapor Deposition (MOCVD) and other material science applications.

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Carbon versus Silicon Bridges. Synthesis of a New Versatile Ligand and Its Applications in Organolanthanide Chemistry

Cited by 62 publications

References 60 publications

Tetramethylcyclopentadienyl vs Cyclopentadienyl Substituents. Synthesis and Structural Characterization of Organolanthanide Compounds Derived from the Versatile Ligand Me₂Si(C₅Me₄H)(C₂B₁₀H₁₁)

Tetramethylcyclopentadienyl vs Cyclopentadienyl Substituents. Synthesis and Structural Characterization of Organolanthanide Compounds Derived from the Versatile Ligand Me₂Si(C₅Me₄H)(C₂B₁₀H₁₁)

Synthesis and crystal structures of cyclopentadienyl dimolybdenum carbonyl complexes

Scandium, Yttrium & The Lanthanides: Organometallic ChemistryBased in part on the article Scandium, Yttrium & The Lanthanides: Organometallic Chemistry by R. D. Köhn, G. Kociok‐Köhn, & H. Schumann which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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Carbon versus Silicon Bridges. Synthesis of a New Versatile Ligand and Its Applications in Organolanthanide Chemistry

Cited by 62 publications

References 60 publications

Tetramethylcyclopentadienyl vs Cyclopentadienyl Substituents. Synthesis and Structural Characterization of Organolanthanide Compounds Derived from the Versatile Ligand Me2Si(C5Me4H)(C2B10H11)

Tetramethylcyclopentadienyl vs Cyclopentadienyl Substituents. Synthesis and Structural Characterization of Organolanthanide Compounds Derived from the Versatile Ligand Me2Si(C5Me4H)(C2B10H11)

Synthesis and crystal structures of cyclopentadienyl dimolybdenum carbonyl complexes

Scandium, Yttrium & The Lanthanides: Organometallic ChemistryBased in part on the article Scandium, Yttrium & The Lanthanides: Organometallic Chemistry by R. D. Köhn, G. Kociok‐Köhn, & H. Schumann which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

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Tetramethylcyclopentadienyl vs Cyclopentadienyl Substituents. Synthesis and Structural Characterization of Organolanthanide Compounds Derived from the Versatile Ligand Me₂Si(C₅Me₄H)(C₂B₁₀H₁₁)

Tetramethylcyclopentadienyl vs Cyclopentadienyl Substituents. Synthesis and Structural Characterization of Organolanthanide Compounds Derived from the Versatile Ligand Me₂Si(C₅Me₄H)(C₂B₁₀H₁₁)