Iron(II) and Zinc(II) Complexes with Tetradentate Bis(pyrazolyl)methane Ligands as Catalysts for the Ring-Opening Polymerisation of rac-Lactide

被引：37

作者：

Herber, Ulrich ^{[1
]}

Hegner, Katharina ^{[1
]}

Wolters, Daniel ^{[1
]}

Siris, Rita ^{[2
]}

Wrobel, Karina

Hoffmann, Alexander ^{[1
]}

Lochenie, Charles ^{[1
,3
]}

Weber, Birgit ^{[3
]}

Kuckling, Dirk ^{[4
]}

Herres-Pawlis, Sonja ^{[1
]}

机构：

[1] Rhein Westfal TH Aachen, Inst Inorgan Chem, Landoltweg 1, D-52074 Aachen, Germany

[2] Ludwig Maximilians Univ Munchen, Dept Chem & Pharm, Butenandtstr 5-13, D-81377 Munich, Germany

[3] Univ Bayreuth, Inorgan Chem 2, Univ Str 30, D-95440 Bayreuth, Germany

[4] Univ Paderborn, Dept Chem, Warburger Str 100, D-33098 Paderborn, Germany

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2017年 / 10期

关键词：

N ligands; Iron; Zinc; Ring-opening polymerization; TRANSITION-METAL-COMPLEXES; N; O HETEROSCORPIONATE LIGANDS; DIFFERENT DONOR ABILITIES; PYRIDINE HYBRID LIGANDS; CYCLIC ESTERS; SPECTROSCOPIC PROPERTIES; SCORPIONATE LIGANDS; RUTHENIUM CARBENE; FERRIC ALKOXIDES; POLYLACTONES;

D O I：

10.1002/ejic.201601345

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A new subgroup of bis(pyrazolyl) methane ligands has been developed through the synthesis of the first N, N, N, N-tetradentate bis(pyrazolyl) methane compounds, namely, bis( pyrazolyl) bipyridinylmethane [HC(Pz)(2)Bipy, L1] and bis(3,5methylpyrazolyl) bipyridinylmethane [HC(3,5-MePz)(2)Bipy, L2]. From these ligands, a large variety of new mononuclear Fe-II and Zn-II complexes with counterions ranging from halides to carboxylates and sulfate were synthesised and characterised by X-ray crystallography. The complexes [Fe{HC(Pz)(2)Bipy}X-2] (X = Cl-, CF3CO2-, CF3 SO3-), [Fe{HC(3,5-MePz)(2)Bipy}X-2] (X = Cl-, CF3CO2-) and [Zn{HC(Pz)(2)Bipy}X-2] (X = Cl-, CF3CO2-) were tested in the melt ring-opening polymerisation of sublimed and unsublimed technical-grade rac-lactide at 150 degrees C. The complex [Fe{HC(Pz)(2)Bipy}(CF3CO2)(2)(-)] showed the most promising results and produced a conversion of 87 % after 30 h with molecular weights of M-w approximate to 30000 g mol(-1).

引用

页码：1341 / 1354

页数：14

共 86 条

[1] SYNTHESIS, STRUCTURE, AND SPECTROSCOPIC PROPERTIES OF COPPER(II) COMPOUNDS CONTAINING NITROGEN SULFUR DONOR LIGANDS - THE CRYSTAL AND MOLECULAR-STRUCTURE OF AQUA[1,7-BIS(N-METHYLBENZIMIDAZOL-2'-YL)-2,6-DITHIAHEPTANE]COPPER(II) PERCHLORATE [J].

ADDISON, AW ;

RAO, TN ;

REEDIJK, J ;

VANRIJN, J ;

VERSCHOOR, GC .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1984, (07) :1349-1356

[2] Tl(I), Fe(II), and Co(II) complexes supported by a monoanionic N,N,N′-heteroscorpionate ligand bis(3,5-di-tertbutylpyrazol-1-yl)-1-CH2NAr (Ar=2,6-iPr2C6H3) [J].

Adhikari, D ;

Zhao, GY ;

Basuli, F ;

Tomaszewski, J ;

Huffman, JC ;

Mindiola, DJ .

INORGANIC CHEMISTRY, 2006, 45 (04) :1604-1610

[3] Discrete heteroscorpionate lithium and zinc alkyl complexes.: Synthesis, structural studies, and ROP of cyclic esters [J].

Alonso-Moreno, Carlos ;

Garces, Andres ;

Sanchez-Barba, Luis F. ;

Fajardo, Mariano ;

Fernandez-Baeza, Juan ;

Otero, Antonio ;

Lara-Sanchez, Agustin ;

Antinolo, Antonio ;

Broomfield, Lewis ;

Lopez-Solera, M. Isabel ;

Rodriguez, Ana M. .

ORGANOMETALLICS, 2008, 27 (06) :1310-1321

[4] Structures and spectra of bis-tripodal iron(II) chelates, [FeL2]2+, where L= tris(pyrazol-1-yl)methane, tris(pyridin-2-yl)methane, bis(pyrazol-1-yl)(pyridin-2-yl)methane and tris(pyridin-2-yl)-phosphine oxide.: Magnetism and spin crossover in the (pz)3CH case [J].

Anderson, PA ;

Astley, T ;

Hitchman, MA ;

Keene, FR ;

Moubaraki, B ;

Murray, KS ;

Skelton, BW ;

Tiekink, ERT ;

Toftlund, H ;

White, AH .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2000, (20) :3505-3512

[5]

[Anonymous], ANGEW CHEM

[6]

[Anonymous], 2012, TWINABS VERS 2012 1

[7]

[Anonymous], 2011, SAINT VERS 8 18C SAD

[8] Synthesis of 1,1′-ferrocenediyl salicylaldimine ligands and their application in titanium-initiated lactide polymerization [J].

Atkinson, Robert C. J. ;

Gerry, Kathryn ;

Gibson, Vernon C. ;

Long, Nicholas J. ;

Marshall, Edward L. ;

West, Lara J. .

ORGANOMETALLICS, 2007, 26 (02) :316-320

[9] Bis(pyrazol-1-yl)acetates as tripodal heteroscorpionate Ligands in iron chemistry:: Syntheses and structures of Iron(II) and Iron(III) complexes with bpza, bdmpza, and bdtbpza ligands [J].

Beck, A ;

Barth, A ;

Hubner, E ;

Burzlaff, N .

INORGANIC CHEMISTRY, 2003, 42 (22) :7182-7188

[10] Block Copolymerization of Lactide and an Epoxide Facilitated by a Redox Switchable Iron-Based Catalyst [J].

Biernesser, Ashley B. ;

Delle Chiaie, Kayla R. ;

Curley, Julia B. ;

Byers, Jeffery A. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (17) :5251-5254

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