Co-reporter:Feng Kong;Meng Li;Xigeng Zhou
RSC Advances (2011-Present) 2017 vol. 7(Issue 47) pp:29752-29761
Publication Date(Web):2017/06/05
DOI:10.1039/C7RA04524G
A series of guanidinate rare-earth metal complexes [(PhCH2)2NC(NC6H4iPr2-2,6)2]RE(CH2C6H4NMe2-o)2 (RE = Y (2a), La (2b), Dy (2c), Lu (2d)) were synthesized by the acid–base reaction of RE(CH2C6H4NMe2-o)3 with (PhCH2)2N[C(NHR)(NR)] (R = 2,6-iPr2-C6H3) (1) in THF. Treatment of complexes 2 with two equivalents of carbon dioxide, sulfur and phenyl isothiocyanate gave the corresponding insertion products {[(PhCH2)2NC(NC6H4iPr2-2,6)2]RE(μ-η2:η1-O2CCH2C6H4NMe2-o)(μ-η1:η1-O2CCH2C6H4NMe2-o)}2 (RE = Y (3a), La (3b), Dy (3c), Lu (3d)), {[(PhCH2)2NC(NC6H4iPr2-2,6)2]RE[μ-S(CH2C6H4NMe2-o)]2}2 (RE = Y (4a), La (4b), Dy (4c), Lu (4d)) and {[(PhCH2)2NC(NC6H4iPr2-2,6)2]RE{SC(CH2C6H4NMe2-o)NPh}2 (RE = Y (5a), La (5b), Dy (5c), Lu (5d)) in good yields, respectively. All new complexes were fully characterized by NMR spectroscopy and elemental analysis. The structures of 1, 2d, 3, 4a, 4c–d, 5a, and 5c–d were established by X-ray diffraction studies. Complexes 2 were found to have a high activity and excellent 3,4-selectivity for isoprene polymerization in the presence of [Ph3C][B(C6F5)4].
Co-reporter:Yanfang Wang, Bingwei Chen, Yi Zhang, Lijun Fu, Yusong Zhu, Lixin Zhang, Yuping Wu
Electrochimica Acta 2016 Volume 213() pp:260-269
Publication Date(Web):20 September 2016
DOI:10.1016/j.electacta.2016.07.019
•Necklace architectures with ZIF-8 nanocrystals strung on MWCNTs are obtained.•“Necklace” derived carbons exhibit hierarchical micro-mesoporous structures.•The carbon exhibits excellent rate and cycling capability.•The capacitance retention after 10000 cycles at 10 A·g−1 is 99.7%.•The synergistic interactions contribute to the excellent performances.Carbon materials from zeolitic imidazolate framework (ZIF) present poor electrochemical performance as electrode materials for supercapacitors. In this work, well-intergrown ZIF nanocystals are strung on MWCNTs to form necklace architecture. After carbonization and chemical etching, porous carbons with necklace architecture and proper hierarchical micro-mesoporous structure were obtained. It exhibits excellent electrochemical performance as electrode material for supercapacitor in 1 M H2SO4 solution such as high specific capacitance up to 326 F·g−1 at 1 A·g−1, good rate capability and excellent cycling stability of 99.7% capacitance retention after 10000 cycles. The main reasons are due to the increased surface area, the improved electrical conductivity, and the combination of micro- and meso-porous structure. This provides another promising way to design porous carbons from ZIF materials for supercapacitors.
Co-reporter:Jianquan Hong, Zhenhua Li, Zhening Chen, Linhong Weng, Xigeng Zhou and Lixin Zhang
Dalton Transactions 2016 vol. 45(Issue 15) pp:6641-6649
Publication Date(Web):02 Mar 2016
DOI:10.1039/C6DT00314A
Diverse reactivity patterns of mixed tetramethyl/methylidene rare-earth complexes bearing bulky benzamidinate coligands L3Ln3(μ2-Me)3(μ3-Me)(μ3-CH2) [L = [PhC(NC6H3iPr2-2,6)2]−; Ln = Y(1a), Lu(1b)] with PhCN, alkynes, and CS2 have been established. Reaction of complexes 1 with PhCN gave the μ3-CH2 addition complexes (NCNdipp)3Lu3(μ2-Me)3(μ3-Me)[μ–η1:η1:η3-CH2C(Ph)N] [Ln = Y(2a), Lu(2b)]. Treatment of complexes 1 with phenylacetylene afforded unexpected alkenyl dianion complexes L3Ln3(μ2-Me)3(μ3-Me)(μ–η1:η3-PhCCMe) [Ln = Y(3a), Lu(3b)] through the insertion of rare earth methylidene into a C–H bond in a reductive fashion. However, reaction of complexes 1 and HCCSiMe3 gave μ3-Me protonolysis complexes L3Ln3(μ2-Me)3(μ3-CCSiMe3)(μ3-CH2) [Ln = Y (4a), Lu (4b)] in excellent yields. Treatment of complexes 1 with CS2 led to the formation of the methyl activation complexes L3Ln3(μ2-Me)2(μ3-CH2)(μ3–η1:η2:η2-S2CCH2) [Ln = Y(5a), Lu(5b)]. All the new complexes were fully characterized.
Co-reporter:Kai Wang;Gen Luo;Dr. Jianquan Hong;Dr. Xigeng Zhou;Dr. Linhong Weng;Dr. Yi Luo;Assoc.Dr. Lixin Zhang
Angewandte Chemie 2014 Volume 126( Issue 4) pp:1071-1074
Publication Date(Web):
DOI:10.1002/ange.201307422
Abstract
Two new trinuclear μ3-bridged rare-earth metal phosphinidene complexes, [{L(Ln)(μ-Me)}3(μ3-Me)(μ3-PPh)] (L=[PhC(NC6H4iPr2-2,6)2]−, Ln=Y (2 a), Lu (2 b)), were synthesized through methane elimination of the corresponding carbene precursors with phenylphosphine. Heating a toluene solution of 2 at 120 °C leads to an unprecedented ortho CH bond activation of the PhP ligand to form the bridged phosphinidene/phenyl complexes. Reactions of 2 with ketones, thione, or isothiocyanate show clear phospha-Wittig chemistry, giving the corresponding organic phosphinidenation products and oxide (sulfide) complexes. Reaction of 2 with CS2 leads to the formation of novel trinuclear rare-earth metal thione dianion clusters, for which a possible pathway was determined by DFT calculation.
Co-reporter:Kai Wang;Gen Luo;Dr. Jianquan Hong;Dr. Xigeng Zhou;Dr. Linhong Weng;Dr. Yi Luo;Assoc.Dr. Lixin Zhang
Angewandte Chemie International Edition 2014 Volume 53( Issue 4) pp:1053-1056
Publication Date(Web):
DOI:10.1002/anie.201307422
Abstract
Two new trinuclear μ3-bridged rare-earth metal phosphinidene complexes, [{L(Ln)(μ-Me)}3(μ3-Me)(μ3-PPh)] (L=[PhC(NC6H4iPr2-2,6)2]−, Ln=Y (2 a), Lu (2 b)), were synthesized through methane elimination of the corresponding carbene precursors with phenylphosphine. Heating a toluene solution of 2 at 120 °C leads to an unprecedented ortho CH bond activation of the PhP ligand to form the bridged phosphinidene/phenyl complexes. Reactions of 2 with ketones, thione, or isothiocyanate show clear phospha-Wittig chemistry, giving the corresponding organic phosphinidenation products and oxide (sulfide) complexes. Reaction of 2 with CS2 leads to the formation of novel trinuclear rare-earth metal thione dianion clusters, for which a possible pathway was determined by DFT calculation.
Co-reporter:Meng Li, Jianquan Hong, Zhenxia Chen, Xigeng Zhou and Lixin Zhang
Dalton Transactions 2013 vol. 42(Issue 23) pp:8288-8297
Publication Date(Web):03 Apr 2013
DOI:10.1039/C3DT33040K
A series of phenylenediamidinate rare earth metal complexes 1,4-C6H4[C(NR)2Ln(o-CH2C6H4NMe2)2]2 (R = 2,6-iPr2-C6H3, Ln = Y (2a), Lu (2b), Sc (2c)) were synthesized by deprotonation of 1,4-C6H4[C(NR)(NHR)]2 (1) with two equivalents of n-BuLi followed by reacting with two equivalents of anhydrous LnCl3 and subsequently four equivalents of Li(o-CH2C6H4NMe2), or by protolysis of [Ln(o-CH2C6H4NMe2)3] with 0.5 equivalent of 1 in THF or toluene. Treatment of complexes 2a and 2b with four equivalents of phenyl isocyanate and phenyl isothiocyanate gave the corresponding insertion products 1,4-C6H4[C(NR)2Ln{OC(CH2C6H4NMe2-o)NPh}2(THF)]2 (Ln = Y (3a), Lu (3b)) and 1,4-C6H4[C(NR)2Ln{SC(CH2C6H4NMe2-o)NPh}2]2 (Ln = Y (4a), Lu (4b)), respectively. The structures of 1, 3b, and 4a were established by X-ray diffraction studies. Complexes 2 show high activity for rac-lactide and ε-caprolactone polymerization; for the former a synergistic effect between two metal centers is observed.
Co-reporter:Dr. Jianquan Hong;Dr. Lixin Zhang;Kai Wang;Yin Zhang; Linhong Weng ; Xigeng Zhou
Chemistry - A European Journal 2013 Volume 19( Issue 24) pp:
Publication Date(Web):
DOI:10.1002/chem.201390085
Co-reporter:Dr. Jianquan Hong;Dr. Lixin Zhang;Kai Wang;Yin Zhang; Linhong Weng ; Xigeng Zhou
Chemistry - A European Journal 2013 Volume 19( Issue 24) pp:7865-7873
Publication Date(Web):
DOI:10.1002/chem.201300440
Abstract
Three new patterns of reactivity of rare-earth metal methylidene complexes have been established and thus have resulted in access to a wide variety of imido rare-earth metal complexes [L3Ln3(μ2-Me)3(μ3-Me)(μ-NR)] (L=[PhC(NC6H3iPr2-2,6)2]−; R=Ph, Ln=Y (2 a), Lu (2 b); R=2,6-Me2C6H3, Ln=Y (3 a), Lu (3 b); R=p-ClC6H4, Ln=Y (4 a), Lu (4 b); R=p-MeOC6H4, Ln=Y (5 a), Lu (5 b); R=Me2CHCH2CH2, Ln=Y (6 a), Lu (6 b)) and [{L3Lu3(μ2-Me)3(μ3-Me)}2(μ-NR′N)] (R′=(CH2)6 (7 b), (C6H4)2 (8 b)). Complex 2 b was treated with an excess of CO2 to give the corresponding carboxylate complex [L3Lu3(μ-η1:η1-O2CCH3)3(μ-η1:η2-O2C-CH3)(μ-η1:η1:η2-O2CNPh)] (9 b) easily. Complex 2 a could undergo the selective μ3-Me abstraction reaction with phenyl acetylene to give the mixed imido/alkynide complex [L3Y3(μ2-Me)3(μ3-η1:η1:η3-NPh)(μ3-CCPh)] (10 a) in high yield. Treatment of 2 with one equivalent of thiophenol gave the selective μ3-methyl-abstracted products [L3Ln3(μ2-Me)3(μ3-η1:η1:η3-NPh)(μ3-SPh)] (Ln=Y (11 a); Lu (11 b). All new complexes have been characterized by elemental analysis, NMR spectroscopy, and most of the structures confirmed by X-ray diffraction.
Co-reporter:Jianquan Hong, Lixin Zhang, Kai Wang, Zhenxia Chen, Limin Wu, and Xigeng Zhou
Organometallics 2013 Volume 32(Issue 24) pp:7312-7322
Publication Date(Web):December 2, 2013
DOI:10.1021/om400787j
Three kinds of solvated lithium amidinates with different coordination models were obtained via recrystallization of [PhC(NC6H4iPr2-2,6)2]Li(THF) (1a) in different solvents. Treatment of o-Me2NC6H4CH2Li with LLnCl2(THF)n (2; L = [PhC(NC6H4iPr2-2,6)2]− (NCNdipp), [o-Me2NC6H4CH2C(NC6H4iPr2-2,6)2]− (NCNdipp′)) formed in situ from reaction of LnCl3(THF)x with LLi(THF) gave the rare-earth-metal bis(aminobenzyl) complexes LLn(CH2C6H4NMe2-o)2 (L = NCNdipp, Ln = Sc (3a), Y (3b), Lu (3c); L = NCNdipp′, Ln = Sc (3d), Lu (3e)) in high yields. Reactions of complexes 3 with CO2, PhNCO, 2,6-diisopropylaniline, and S have been explored. CO2 inserted into each Ln–C bond of complexes 3a–c to form the dual-core complexes [(NCNdipp)Sc(μ-η1:η1-O2CCH2C6H4NMe2-o)2]2 (4a) and [(NCNdipp)Ln(μ-η1:η2-O2CCH2C6H4NMe2-o)(μ-η1:η1-O2CCH2C6H4NMe2-o)]2 (Ln = Y (4b), Lu (4c)). The reaction of 3b,c,e with PhNCO produced LLu[OC(CH2C6H4NMe2-o)NPh]2(thf) (L = NCNdipp, Ln = Y (5b), Lu (5c); L = NCNdipp′, Ln = Lu (5e)). Protonolysis of 3a,b by 2,6-diisopropylaniline formed straightforwardly the μ2-imido complexes [(NCNdipp)Ln(μ-NC6H4iPr2-2,6)]2 (Ln = Sc (6a), Lu (6c)). Reaction of 3e with S8 afforded the sulfur insertion products (NCNdipp′)Lu(CH2C6H4NMe2-o)(SCH2C6H4NMe2-o)(thf) (7e) and (NCNdipp′)Lu(SCH2C6H4NMe2-o)2(thf)2 (7f) in high yields, respectively, depending on the stoichiometric ratio. All of these complexes were fully characterized by elemental analysis, NMR spectroscopy, and X-ray structural determinations.
Co-reporter:Jianquan Hong;Dr. Lixin Zhang;Xiaying Yu;Meng Li;Dr. Zhengxing Zhang;Dr. Pengzhi Zheng;Dr. Masayoshi Nishiura;Dr. Zhaomin Hou;Dr. Xigeng Zhou
Chemistry - A European Journal 2011 Volume 17( Issue 7) pp:2130-2137
Publication Date(Web):
DOI:10.1002/chem.201002670
Abstract
Unsolvated, trinuclear, homometallic, rare-earth-metal multimethyl methylidene complexes [{(NCN)Ln(μ2-CH3)}3(μ3-CH3)(μ3-CH2)] (NCN=L=[PhC{NC6H4(iPr-2,6)2}2]−; Ln=Sc (2 a), Lu (2 b)) have been synthesized by treatment of [(L)Ln{CH2C6H4N(CH3)2-o}2] (Ln=Sc (1 a), Lu (1 b)) with two equivalents of AlMe3 in toluene at ambient temperature in good yields. Treatment of 1 with three equivalents of AlMe3 gives the heterometallic trinuclear complexes [(L)Ln(AlMe4)2] (Ln=Sc (3 a), Lu (3 b)) in good yields. Interestingly, 2 can also be generated by recrystallization of 3 in THF/toluene, thereby indicating that the THF molecule can also induce CH bond activation of 2. Reaction of 2 with one equivalent of ketones affords the trinuclear homometallic oxo–trimethyl complexes [{(L)Ln(μ2-CH3)}3(μ3-CH3)(μ3-O)] (Ln=Sc(4 a), Lu(4 b)) in high yields. Complex 4 b reacts with one equivalent of cyclohexanone to give the methyl abstraction product [{(L)Lu(μ2-CH3)}3(μ3-OC6H9)(μ3-O)] (5 b), whereas reaction of 4 b with acetophenone forms the insertion product [{(L)Lu(μ2-CH3)}3{μ3-OCPh(CH3)2}(μ3-O)] (6 b). Complex 4 a is inert to ketone under the same conditions. All these new complexes have been characterized by elemental analysis, NMR spectroscopy, and confirmed by X-ray diffraction determination.
Co-reporter:Jianquan Hong, Zhenhua Li, Zhening Chen, Linhong Weng, Xigeng Zhou and Lixin Zhang
Dalton Transactions 2016 - vol. 45(Issue 15) pp:NaN6649-6649
Publication Date(Web):2016/03/02
DOI:10.1039/C6DT00314A
Diverse reactivity patterns of mixed tetramethyl/methylidene rare-earth complexes bearing bulky benzamidinate coligands L3Ln3(μ2-Me)3(μ3-Me)(μ3-CH2) [L = [PhC(NC6H3iPr2-2,6)2]−; Ln = Y(1a), Lu(1b)] with PhCN, alkynes, and CS2 have been established. Reaction of complexes 1 with PhCN gave the μ3-CH2 addition complexes (NCNdipp)3Lu3(μ2-Me)3(μ3-Me)[μ–η1:η1:η3-CH2C(Ph)N] [Ln = Y(2a), Lu(2b)]. Treatment of complexes 1 with phenylacetylene afforded unexpected alkenyl dianion complexes L3Ln3(μ2-Me)3(μ3-Me)(μ–η1:η3-PhCCMe) [Ln = Y(3a), Lu(3b)] through the insertion of rare earth methylidene into a C–H bond in a reductive fashion. However, reaction of complexes 1 and HCCSiMe3 gave μ3-Me protonolysis complexes L3Ln3(μ2-Me)3(μ3-CCSiMe3)(μ3-CH2) [Ln = Y (4a), Lu (4b)] in excellent yields. Treatment of complexes 1 with CS2 led to the formation of the methyl activation complexes L3Ln3(μ2-Me)2(μ3-CH2)(μ3–η1:η2:η2-S2CCH2) [Ln = Y(5a), Lu(5b)]. All the new complexes were fully characterized.
Co-reporter:Meng Li, Jianquan Hong, Zhenxia Chen, Xigeng Zhou and Lixin Zhang
Dalton Transactions 2013 - vol. 42(Issue 23) pp:NaN8297-8297
Publication Date(Web):2013/04/03
DOI:10.1039/C3DT33040K
A series of phenylenediamidinate rare earth metal complexes 1,4-C6H4[C(NR)2Ln(o-CH2C6H4NMe2)2]2 (R = 2,6-iPr2-C6H3, Ln = Y (2a), Lu (2b), Sc (2c)) were synthesized by deprotonation of 1,4-C6H4[C(NR)(NHR)]2 (1) with two equivalents of n-BuLi followed by reacting with two equivalents of anhydrous LnCl3 and subsequently four equivalents of Li(o-CH2C6H4NMe2), or by protolysis of [Ln(o-CH2C6H4NMe2)3] with 0.5 equivalent of 1 in THF or toluene. Treatment of complexes 2a and 2b with four equivalents of phenyl isocyanate and phenyl isothiocyanate gave the corresponding insertion products 1,4-C6H4[C(NR)2Ln{OC(CH2C6H4NMe2-o)NPh}2(THF)]2 (Ln = Y (3a), Lu (3b)) and 1,4-C6H4[C(NR)2Ln{SC(CH2C6H4NMe2-o)NPh}2]2 (Ln = Y (4a), Lu (4b)), respectively. The structures of 1, 3b, and 4a were established by X-ray diffraction studies. Complexes 2 show high activity for rac-lactide and ε-caprolactone polymerization; for the former a synergistic effect between two metal centers is observed.
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