Probing the Effect of Organic and Organometallic Functionalization on [1,5]-Silicon Shifts in Indenylsilanes

Stradiotto, Mark; Hazendonk, Paul; Bain, Alex D.; Brook, and Michael A.; McGlinchey, Michael J.

doi:10.1021/om990650f

Cited by 22 publications

(13 citation statements)

References 90 publications

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“…A similar result was observed by Okuda and co-workers, who reported an oxidative coupling of a trimethylsilyl-substituted cyclopentadienide anion by iron(III) chloride . Stradiotto et al recently observed an oxidative coupling in the study of [1,5]-silicon shifts in indenylsilanes leading to isolation and characterization of the dimer [C 18 H 10 (SiMe 3 ) 2 ] 2 …”

Section: Resultssupporting

confidence: 80%

Coordination and Reactivity Diversity ofN-Piperidineethyl-Functionalized Indenyl Ligands: Synthesis, Structure, Theoretical Calculation, and Catalytic Activity of Organolanthanide Complexes with the Ligands

et al. 2007

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The interactions of N-piperidineethyl-functionalized indene compounds 1-R-3-C 5 H 10 NCH 2 CH 2 C 9 H 6 (R ) H-(1), Me 3 Si-( 2)) with lanthanide(III) amides [(Me 3 Si) 2 N] 3 Ln(µ-Cl)Li(THF) 3 (Ln ) Yb, Eu, Sm, Nd) were studied. The results indicated that the ligands and reductive potentials of Ln 3+ /Ln 2+ have an influence on the reaction patterns and the coordination mode of the indenyl ligands with the central metals. Reactions of [(Me 3 Si) 2 N] 3 Ln(µ-Cl)Li(THF) 3 (Ln ) Yb, Eu) with 2 equiv of corresponding indene compounds 1-R-3-C 5 H 10 NCH 2 CH 2 C 9 H 6 (R ) H-(1), Me 3 Si-(2)) produced organolanthanide(II) complexes [η 5 :η 1 -C 5 H 10 NCH 2 CH 2 C 9 H 6 ] 2 Ln II (Ln ) Yb (3), Eu (5)) and novel organolanthanide(II) complexes with general formula [η 4 :η 4), Eu ( 6)), and a new highly conjugated bis(N-piperidineethyl)dibenzofulvalene, (C 5 H 10 NCH 2 CH 2 C 9 H 5 ) 2 ( 9), was unexpectedly isolated as a byproduct in the preparation of 6, indicating the ligands' effects on the coordination and reactivity patterns. Theoretical calculations on ytterbium(II) complexes having indenyl ligands indicated that the indenyl hapticity depends on the strain, steric, and electronic effects. Treatment of lanthanide(III) amides [(Me 3 Si) 2 N] 3 Ln(µ-Cl)Li(THF) 3 (Ln ) Sm, Nd) with 2 equiv of C 5 H 10 NCH 2 CH 2 C 9 H 7 (1) afforded indenyl lanthanide(III) complexes with general formula [η 3 -C 5 H 10 NCH 2 CH 2 C 9 H 6 ] 2 Ln III [η 3 :η 1 -C 5 H 10 NCH 2 CH 2 C 9 H 6 ] (Ln ) Sm (7), Nd (8)). The shortest distances involving the nonbridging atoms of the C 5 portions of the indenyl groups indicated an allyl-like nature of the ligand-to-metal coordination. The interaction of [(Me 3 Si) 2 N] 3 Sm III (µ-Cl)Li-(THF) 3 with 2 equiv of 1-Me 3 Si-3-C 5 H 10 NCH 2 CH 2 C 9 H 6 (2) produced an unexpected bis(N-piperidineethyl)dibenzofulvalene (C 5 H 10 NCH 2 CH 2 C 9 H 5 ) 2 (9) and other unidentified solids, suggesting the ligands' influence on the reactivity patterns. All the compounds were fully characterized by spectroscopic methods and elemental analyses. The structures of compounds 4, 7, 8, and 9 were additionally determined by X-ray diffraction study. The catalytic activity of the organolanthanide complexes 3-8 on MMA polymerization was examined. It was found that the π-bonded tris(N-piperidineethylindenyl)lanthanide(III) complexes 7 and 8 exhibit unexpected good catalytic activity on MMA polymerization, and complex 7 also showed an unexpected high catalytic activity on ε-caprolactone polymerization. It was found that the catalytic activity of the complexes depended on the polymerization conditions. The solvents, temperatures, substituted groups, and lanthanide ionic radii effects on the catalytic activity of the complexes were examined.

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Section: Resultssupporting

confidence: 80%

Coordination and Reactivity Diversity ofN-Piperidineethyl-Functionalized Indenyl Ligands: Synthesis, Structure, Theoretical Calculation, and Catalytic Activity of Organolanthanide Complexes with the Ligands

et al. 2007

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“…[22] The reductive elimination from a Ni IV intermediate (step c) is also quite reasonable, as is the rearrangement of the initially formed 1-phenyl-1,3-bis(trimethysilyl)indene to the observed 3-phenyl-1,3-bis(trimethysilyl)indene isomer by a silyl migration (step e). [23] Finally, comproportionation of Ni II and Ni 0 species to give Ni I dimers (step d) has been reported, [24] although the origin of the putative "Ni 0 (PPh 3 ) 2 " fragment is not known at this point.…”

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confidence: 99%

Tetraphenylborate as a Novel Bridging Ligand in a Zwitterionic Nickel(I) Dimer

2005

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Heterolytic abstraction of anionic ligands such as halides or alkyl substituents can convert coordinatively saturated organometallic complexes into highly electrophilic, usually transient, cationic species that can serve as efficient initiators in various catalytic reactions. This strategy has been used in the development of many catalytic processes based on (quasi) square-planar d 8 metal precursors, including the recently reported systems for olefin polymerization reactions. [1] In this context, we have shown that abstraction of Cl À from the complexes [(R-ind)Ni(PPh 3 )Cl] (R-ind = indenyl and its substituted derivatives) [2] leads to the generation of a transient species (presumed to be [(R-ind)Ni(PPh 3 )] + ) that reacts with excess substrate to promote the oligomerization or polymerization of various olefins, [3] PhCCH, [4] and PhSiH 3 , [5] or catalyzes the hydrosilylation of olefins and ketones [6]

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“…Interaction between D / D′ and in situ generated carbodiimide affords F . 1,5-Sigmatropic rearrangement over the indenyl ring followed by an intramolecular proton shift gives the final product 11a…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structural Characterization, and Reactivity of Group 4 Metal Complexes Derived from 1-Indenyl-1,2-carborane

2008

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Treatment of 1-indenyl-1,2-carborane with 1 equiv of M(NMe 2 ) 4 (M ) Zr, Hf) in toluene gave [η 5 -(C 2 B 10 H 11 )C 9 H 6 ]M(NMe 2 ) 3 (2), which were converted to [η 5 -(C 9 H 7 )C 2 B 9 H 10 ]M(NMe 2 ) 2 (HNMe 2 ) (3) in the presence of HNMe 2 . Complexes 3 were also prepared from an equimolar reaction of [Me 3 NH][7-C 9 H 7 -7,8-C 2 B 9 H 11 ] (4) with M(NMe 2 ) 4 . Dissolving 2 or 3 in polar solvents led to the isolation of structurally unique complexes [σ:Ti, Zr, Hf; NR 2 ) NMe 2 , NEt 2 , N(CH 2 ) 4 ) were prepared from reactions of 3 or 5b with 3 equiv of guanidines in refluxing THF. Treatment of 5b with 1 equiv of diphenylketene generated [σ:η 5 -{[3-C(dCPh 2 )-O]C 9 H 6 }C 2 B 9 H 10 ]Zr(NMe 2 )(THF) 2 ( 14). These complexes were fully characterized by various spectroscopic techniques and elemental analyses. Some were further confirmed by single-crystal X-ray analyses.

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Probing the Effect of Organic and Organometallic Functionalization on [1,5]-Silicon Shifts in Indenylsilanes

Cited by 22 publications

References 90 publications

Coordination and Reactivity Diversity ofN-Piperidineethyl-Functionalized Indenyl Ligands: Synthesis, Structure, Theoretical Calculation, and Catalytic Activity of Organolanthanide Complexes with the Ligands

Coordination and Reactivity Diversity ofN-Piperidineethyl-Functionalized Indenyl Ligands: Synthesis, Structure, Theoretical Calculation, and Catalytic Activity of Organolanthanide Complexes with the Ligands

Tetraphenylborate as a Novel Bridging Ligand in a Zwitterionic Nickel(I) Dimer

Synthesis, Structural Characterization, and Reactivity of Group 4 Metal Complexes Derived from 1-Indenyl-1,2-carborane

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