- Solubility determination and thermodynamic analysis of organic zinc supported by β-diimine ligands in pure solvents
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In this work, a static analysis method was used to determine the solubility data of β-diimine ligand (1) (L1 = HC(CMeNAr)2, Ar = 2,6-Me2C6H3), and organic zinc compounds: L1ZnEt (2), L
- Liu, Yi,Li, Mengyao,Sahoo, Somarupa,Ma, Xiaoli
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- Palladium-Catalysed C?H Bond Zincation of Arenes: Scope, Mechanism, and the Role of Heterometallic Intermediates
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Catalytic methods that transform C?H bonds into C?X bonds are of paramount importance in synthesis. A particular focus has been the generation of organoboranes, organosilanes and organostannanes from simple hydrocarbons (X=B, Si, Sn). Despite the importan
- Gar?on, Martí,Mun, Nicolette Wee,White, Andrew J. P.,Crimmin, Mark R.
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supporting information
p. 6145 - 6153
(2021/02/09)
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- Zinc Complexes with an Ethylene-Bridged Bis(β-diketiminate) Ligand: Syntheses, Structures, and Applications as Catalysts in the Borylation of Aryl Iodides
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A dinucleating bis(β-diketiminate) ligand with a flexible bridge has been employed to synthesize zinc complexes. The ligand, abbreviated H2L (H2L = N-(4-((2-((4-((2,6-diisopropylphenyl)imino)pent-2-en-2-yl)amino)ethyl)imino)pent-2-en-2-yl)-2,6-diisopropylaniline), was deprotonated with ZnEt2 to afford [LZn2Et2] (1). Reactions of 1 with 2 equiv of BnOH and nBuOH, respectively, gave access to [LZn2(OBn)2]·C6H14 (2·C6H14) and [LZn2(OnBu)2] (3). Treatment of 1 with 2 equiv of I2 in THF produced [LZn2I2(THF)2]·2THF (4·2THF). X-ray single-crystal diffraction analyses revealed that they are all heteroleptic bimetallic compounds with two metal centers being chelated by one ligand set. The structurally similar compounds 1 and 4·2THF possess approximate C2 symmetry, with two β-diketiminate units being arrayed in head-to-tail antiparallel mode. Thus, the molecular structures of 1 and 4·2THF exhibit a seesaw-like topology. The structures of 2·C6H14 and 3 are almost identical, in which two zinc atoms are shared by two ZnN2C3 six-membered rings, two Zn2ON2C2 seven-membered rings, and one Zn2O2 four-membered ring. Therefore, the metal cores of 2·C6H14 and 3 display a crownlike topology. All complexes are catalytically active for the borylation of aryl iodides with B2Pin2 (B2Pin2 = 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis(1,3,2-dioxaborolane). Complex 1 shows higher activity in comparison to 2, 3, and 4·2THF. The borylation reactions catalyzed by 1 could proceed under mild conditions and can be applied to a series of substrates with high functional group generality. This methodology thus represents a novel use of β-diketiminate zinc complexes for C-I borylation.
- Li, Yafei,Dang, Yan,Li, Dawei,Pan, Huifen,Zhang, Liang,Wang, Li,Cao, Zhu,Li, Yahong
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supporting information
p. 482 - 489
(2021/03/01)
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- The ethylsulfinate ligand: A highly efficient initiating group for the zinc β-diiminate catalyzed copolymerization reaction of CO2 and epoxides
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The quantitative synthesis of a series of new zinc(II) sulfinate complexes (4a-e) by insertion of SO2 into zinc-ethyl bonds of β-diiminate complexes ((ArN=C(CH3)CH=(CH3)CNAr)Zn(O(S=O)Et); Ar = 2,6-diisopropylphenyl (4a), 2
- Eberhardt, Robert,Allmendinger, Markus,Luinstra, Gerrit A.,Rieger, Bernhard
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p. 211 - 214
(2008/10/08)
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- Single-site β-diiminate zinc catalysts for the alternating copolymerization of CO2 and epoxides: Catalyst synthesis and unprecedented polymerization activity
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Synthetic routes to zinc β-diiminate complexes are reported. The synthesis of 11 β-diimine [(BDI)-H] ligands, with varying N-aryl substituents and bridging structures, is described. These ligands are converted to (BDI)ZnX complexes (X = OAc, Et, N(SiMe3)2, Br, Cl, OH, OMe, OiPr). X-ray structural data revealed that all zinc complexes examined exist as μ-X-bridged dimers in the solid state, with the exception of the zinc ethyl and amido complexes which were monomeric. Complexes of the form (BDI)ZnOR (R = alkyl, acyl) and (BDI)ZnN(SiMe3)2 are highly active catalysts for the alternating copolymerization of epoxides and CO2. Copolymerizations of cyclohexene oxide (CHO) and CO2 with (BDI-1)ZnX [(BDI-1) = 2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-pentene)] and (BDI-2)ZnX [(BDI-2) = 2-((2,6-diethylphenyl-amido)-4-((2,6-diethylphenyl)imino)-2-pentene)], where X = OAc, Et, N(SiMe3)2, Br, Cl, OH, OMe, OiPr, were attempted at 50 °C and 100 psi CO2. Complexes with X = OAc, N(SiMe3)2, OMe, OiPr all produced polycarbonate by the alternated insertion of CHO and CO2 with similar catalytic activities, comparable molecular weights, and narrow molecular weight distributions (MWD ~ 1.1), indicating the copolymerizations are living. Furthermore, ligand effects were shown to dramatically influence the polymerization activity as minor steric changes accelerated or terminated the polymerization activity.
- Cheng,Moore,Reczek,Chamberlain,Lobkovsky,Coates
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p. 8738 - 8749
(2007/10/03)
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- Polymerization of lactide with zinc and magnesium β-diiminate complexes: Stereocontrol and mechanism
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A series of zinc(II) and magnesium(II) alkoxides based upon a β-diiminate ligand framework has been prepared. [(BDI-1)ZnOiPr]2 [(BDI-1) = 2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-pentene] exhibited the high
- Chamberlain,Cheng,Moore,Ovitt,Lobkovsky,Coates
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p. 3229 - 3238
(2007/10/03)
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