1,2-Cyclopentadienyl Diimine−Group 13 Complexes

Ong, Christopher M.; Stephan, Douglas W.

doi:10.1021/ic9903782

Cited by 7 publications

(7 citation statements)

References 11 publications

(17 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For 2A , C 6 F 5 group transfer from MeB(C 6 F 5 )

_{−}^{3}

to the aluminum cation gives a quantitative 1:1 mixture of LAlMe(C 6 F 5 ) and MeB(C 6 F 5 ) 2 . Similar activation trends and decomposition processes are operative for AlR 2 compounds incorporating aminotroponiminate,23, 25 β‐diketiminate,42–44, 46 and 1,2‐cyclopentadienyl‐diimine39 ligands. The latter are reportedly unstable as cations even in the presence of donor solvents.…”

Section: Resultsmentioning

confidence: 70%

“…Although aluminum‐based olefin polymerization systems are yet to be well understood, their discovery has prompted an increased interest in the use of ligated, cationic aluminum complexes for catalytic applications. In addition to a large synthetic effort in the area of tetradentate, N,N ′ ,O,O ′‐ligated SALEN complexes,11 the recent organometallic literature has featured reports of many new alkylaluminum compounds bearing bidentate and tridentate N,N ′‐, N,S ‐, or N,O ‐donor ligands 37–51. These species have the potential to function as very active catalysts because of their less coordinatively saturated nature.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Polymerization of methyl methacrylate and other polar monomers with alkylaluminum initiators bearing bidentate and tridentate N‐ and O‐donor ligands

Baugh

Sissano

2002

J. Polym. Sci. A Polym. Chem.

View full text Add to dashboard Cite

Dimethylaluminum complexes bearing bidentate amidate, oxypyridine, and salicylaldimine N,O‐ligands and tridentate N,N′,N″‐pyridyliminoamide ligands were synthesized and spectroscopically characterized. The complexes were investigated in both neutral and borane‐activated cationic forms, along with bidentate N,N′‐ligated aluminum amidinates, as catalysts for the polymerization of methyl methacrylate, ϵ‐caprolactone, and propylene oxide. The neutral complexes generally did not carry out polymerization, but the polymerization/oligomerization of all three monomers was achieved when the various catalysts were activated with B(C6F5)3 or [Ph3C]+[B(C6F5)4]−. The N,O‐ligated cations were much less active for polymerization than the analogous, more stable N,N′‐ligated amidinate cations; both types of cationic complexes catalyzed the ring‐opening cationic polymerization of tetrahydrofuran. B(C6F5)3 and [Ph3C]+[B(C6F5)4]− also independently carried out the oligomerization of propylene oxide. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1633–1651, 2002

show abstract

“…For 2A , C 6 F 5 group transfer from MeB(C 6 F 5 )

_{−}^{3}

Section: Resultsmentioning

confidence: 70%

Section: Introductionmentioning

confidence: 99%

Polymerization of methyl methacrylate and other polar monomers with alkylaluminum initiators bearing bidentate and tridentate N‐ and O‐donor ligands

Baugh

Sissano

2002

J. Polym. Sci. A Polym. Chem.

View full text Add to dashboard Cite

show abstract

“…Closer investigation of the coordination chemistry of 6-aminofulvene-2-aldiminate ligands began in 1998 with the discovery of a straightforward synthesis of the C-phenyl-substituted precursor C5H3[1,2-C(Ph)NH]2H based on the reaction of magnesocene with benzonitrile. The ligand C5H3[1,2-C(Ph)NH]2H was successfully employed in a number of complexes with Mg [25], Al, Ga [26] and Zr [25]. In all these compounds, the 6-aminofulvene-2-aldiminate anion acts as a As a consequence of this resonance, a 6-aminofulvene-2-aldiminate ligand can coordinate to a metal atom in a chelating mode through the two imine nitrogen donors as a fulvenealdiminate (A) or in an η 5 -mode as a cyclopentadienyldiimine.…”

Section: Scheme 4 Resonance Forms Of the [C5h3{c(nhmentioning

confidence: 99%

“…In all these compounds, the 6-aminofulvene-2-aldiminate anion acts as a As a consequence of this resonance, a 6-aminofulvene-2-aldiminate ligand can coordinate to a metal atom in a chelating mode through the two imine nitrogen donors as a fulvenealdiminate (A) or in an η 5 -mode as a cyclopentadienyldiimine. Complexes of this ligand system have been reported for some main group metals, as well as first and second row transition metals [25][26][27][28][29][30][31][32]. Closer investigation of the coordination chemistry of 6-aminofulvene-2-aldiminate ligands began in 1998 with the discovery of a straightforward synthesis of the C-phenyl-substituted precursor C 5 H 3 [1,2-C(Ph)NH] 2 H based on the reaction of magnesocene with benzonitrile.…”

Section: Scheme 4 Resonance Forms Of the [C5h3{c(nhmentioning

confidence: 99%

Unexpected Formation and Structural Characterization of a Dinuclear Sodium Half-Sandwich Complex

et al. 2018

View full text Add to dashboard Cite

Treatment of N,N-diisopropylcarbodiimide with sodium cyclopentadienide (NaCp) in a molar ratio of 1:1 in THF solution resulted in formation of the unexpected dinuclear sodium half-sandwich complex [NaC 5 H 3 {C(NH i Pr)(=N i Pr)} 2-1,2] 2 (1) as colorless crystals in low yield. The newly formed ligand, which belongs to the group of 6-aminofulvene-2-aldiminate ligands, coordinates to sodium in an η 5-coordination mode via the cyclopentadienyl ring. Dimerization occurs through additional chelating κN,N-coordination of the amidine substituents. The NMR data of 1 indicated a slow dimer/monomer equilibrium in solution. A serendipitously isolated hydrolysis product, {µ-(i PrNH) 2 C=O} 2 [NaC 5 H 3 {C(NH i Pr)(=N i Pr)} 2-1,2] 2 (2), contains the new 6-aminofulvene-2-aldiminate ligand in the N,N-chelating coordination mode with the cyclopentadiene ring being uncoordinated. In this case, dimerization occurs through the presence of two bridging neutral N,N-diisopropylurea ligands. Both compounds have been structurally characterized by single-crystal X-ray diffraction.

show abstract

“…The relationship between structure of the catalytic complexes and stereoselectivity of the polymerization has been investigated and elucidated [6][7][8][9][10]22]. Recent organometallic literature has featured reports of many alkylaluminum compounds bearing bidentate N,N-, N,S-, or N,O-donor ligands [23][24][25][26][27][28][29][30]. These species have the potential to function as active catalysts because of their less coordinatively saturated nature.…”

Section: Dimethyl(salicilaldiminato)aluminum Complexesmentioning

confidence: 99%

Aluminum Alkyl Complexes Bearing Salicylaldiminato Ligands: Versatile Initiators in the Ring-Opening Polymerization of Cyclic Esters

Fuoco

Pappalardo

2017

Catalysts

View full text Add to dashboard Cite

Linear aliphatic polyesters are degradable thermoplastic polymers, which can be obtained by ring-opening polymerization (ROP) of cyclic esters through a coordination-insertion mechanism. Aluminum based organometallic complexes have a leading position as efficient catalysts for this polymerization process. Aluminumalkyl complexes bearing salicylaldiminato ligands, although less explored, have been shown to be efficient and versatile catalysts for the ROP of various cyclic esters. These species have the potential to function as active catalysts in the ROP because of their less coordinatively saturated nature with respect to analogous SALEN-type complexes. They have been used as efficient catalysts in the ROP of commercially available cyclic esters, such as ε-caprolactone, L-lactide, rac-lactide, and glycolide. Moreover, they resulted in efficient catalysts for the ROP of cyclic esters with large ring-size and for the ROP of functionalized lactide. Furthermore, they have been used in the co-and ter-polymerization of various cyclic esters affording well controlled polymerization and a plethora of microstructural architectures, ranging from random to block to multiblock.

show abstract

1,2-Cyclopentadienyl Diimine−Group 13 Complexes

Cited by 7 publications

References 11 publications

Polymerization of methyl methacrylate and other polar monomers with alkylaluminum initiators bearing bidentate and tridentate N‐ and O‐donor ligands

Polymerization of methyl methacrylate and other polar monomers with alkylaluminum initiators bearing bidentate and tridentate N‐ and O‐donor ligands

Unexpected Formation and Structural Characterization of a Dinuclear Sodium Half-Sandwich Complex

Aluminum Alkyl Complexes Bearing Salicylaldiminato Ligands: Versatile Initiators in the Ring-Opening Polymerization of Cyclic Esters

Contact Info

Product

Resources

About