Accessible ring opening metathesis and atom transfer radical polymerization catalysts based on dimethyl sulfoxide ruthenium(II) complexes bearing N-heterocyclic carbene ligands

被引：9

作者：

Idehara, Andre H. S. ^{[1
]}

Gois, Patrik D. S. ^{[1
]}

Fernandez, Henrique ^{[2
]}

Goi, Beatriz E. ^{[1
]}

Machado, Antonio E. H. ^{[3
]}

Lima-Neto, Benedito S. ^{[2
]}

Carvalho, Valdemiro P., Jr. ^{[1
]}

机构：

[1] UNESP, Univ Estadual Paulista, Fac Ciencias & Tecnol, BR-19060900 Presidente Prudente, SP, Brazil

[2] Univ Sao Paulo, Inst Quim Sao Carlos, BR-13560970 Sao Carlos, SP, Brazil

[3] Univ Fed Uberlandia, Inst Quim, BR-38400902 Uberlandia, MG, Brazil

来源：

MOLECULAR CATALYSIS | 2018年 / 448卷

基金：

巴西圣保罗研究基金会;

关键词：

Ruthenium complexes; ROMP; ATRP; Norbomene; Methyl methacrylate; ROMP; RU; NORBORNENE; ATRP; COMBINATION; INITIATORS; REACTIVITY; AMINES; TANDEM;

D O I：

10.1016/j.mcat.2018.01.032

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Dimethyl sulfoxide ruthenium(11) complexes of N-heterocyclic carbenes derived from cycloalkylamines (cycloallcyl = cyclopentyl (1a), cyclohexyl (1b), cycloheptyl (1c), and cyclooctyl (1d)) were synthesized: [RuCl2(S-dmso)(2)(IPent)] (2a), [RuCl2(S center dot dmso)(2)(IHex)) (2b), (RuCl2(S-dmso)(2)(IHept)) (2c), and [RuCl2(S center dot dmso)(2)(IOct)) (2d). The imidazolium salts 1a-1d were characterized by FTIR, UV-vis, and H-1 and C-13 NMR spectroscopy, while their respective dimethyl sulfoxide ruthenium(II) complexes (2a-2d) were characterized by elemental analysis, FIR, UV-vis, H-1 and C-13 NMR, and cyclic voltammetry. The complexes 2a-2d were evaluated as catalytic precursors for ROMP of norbornene (NBE) and for ATRP of methyl methacrylate (MMA). The polynorbomene (polyNBE) syntheses via ROMP using the complexes 2a-2d as pre-catalysts were evaluated under reaction conditions of [EDA]/[Ru] = 28 (5 mu L), [NBE]/[Ru] = 5000 at 50 degrees C as a function of time. The polymerization of MMA via ATRP was conducted using the complexes 2a-2d in the presence of ethyl 2-bromoisobutyrate (EBiB) as the initiator. All tests were using the molar ratio [MMA]/[EBiB]/[Ru] = 1000/2/1 and conducted at 85 degrees C. The linear correlation of In([MMA](0)/[MMA]) and time clearly indicates that the concentration of radicals remains constant during the polymerization and that the ATRP of MMA mediated by 2a-2d proceeds in a controlled manner.

引用

页码：135 / 143

页数：9

共 50 条

[21] Ligand-Promoted Carbene Insertion into the Aryl Substituent of an N-Heterocyclic Carbene Ligand in Ruthenium-Based Metathesis Catalysts [J].

Galan, Brandon R. ;

Pitak, Mateusz ;

Gembicky, Milan ;

Keister, Jerome B. ;

Diver, Steven T. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (19) :6822-6832

[22] Stereoselective Olefin Ring-Opening Cross Metathesis Catalyzed by Molybdenum Imido Alkylidene N-Heterocyclic Carbene Complexes [J].

Momin, Mohasin ;

Nagy, Gergely M. ;

Buchmeiser, Michael R. .

ADVANCED SYNTHESIS & CATALYSIS, 2019, 361 (24) :5596-5604

[23] Dual catalytic performance of arene-ruthenium amine complexes for norbornene ring-opening metathesis and methyl methacrylate atom-transfer radical polymerizations [J].

Cruz, Thais R. ;

Silva, Eliada A. ;

Oliveira, Douglas P. ;

Martins, Daniele M. ;

Gois, Patrik D. S. ;

Machado, Antonio E. H. ;

Maia, Pedro Ivo S. ;

Goi, Beatriz E. ;

Lima-Neto, Benedito S. ;

Carvalho-Jr, Valdemiro P. .

APPLIED ORGANOMETALLIC CHEMISTRY, 2020, 34 (05)

[24] Biological and Catalytic Applications of Pd(II)-Indenyl Complexes Bearing Phosphine and N-Heterocyclic Carbene Ligands [J].

Bortolamiol, Enrica ;

Isetta, Giacomo ;

Caligiuri, Isabella ;

Demitri, Nicola ;

Paganelli, Stefano ;

Rizzolio, Flavio ;

Scattolin, Thomas ;

Visentin, Fabiano .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2023, 26 (22)

[25] Synthesis and Characterization of Heteroleptic Ni(II) Bipyridine Complexes Bearing Bis(N-heterocyclic carbene) Ligands [J].

Reineke, Mark H. ;

Porter, Tyler M. ;

Ostericher, Andrew L. ;

Kubiak, Clifford P. .

ORGANOMETALLICS, 2018, 37 (03) :448-453

[26] Preparation of a series of Ru(II) complexes with N-heterocyclic carbene ligands for the catalytic transfer hydrogenation of aromatic ketones [J].

Gurbuz, Nevin ;

Ozcan, Emine Ozge ;

Ozdemir, Ismail ;

Cetinkaya, Bekir ;

Sahin, Onur ;

Buyukgungor, Orhan .

DALTON TRANSACTIONS, 2012, 41 (08) :2330-2339

[27] Novel ruthenium(II) N-heterocyclic carbene complexes as catalyst precursors for the ring-opening metathesis polymerization (ROMP) of enantiomerically pure monomers: X-ray structures, reactivity, and quantum chemical considerations [J].

Buchmeiser, Michael R. ;

Wang, Dongren ;

Zhang, Yan ;

Naumov, Sergej ;

Wurst, Klaus .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2007, (25) :3988-4000

[28] Cationic versus Neutral RuII-N-Heterocyclic Carbene Complexes as Latent Precatalysts for the UV-Induced Ring-Opening Metathesis Polymerization [J].

Wang, Dongren ;

Wurst, Klaus ;

Buchmeiser, Michael R. .

CHEMISTRY-A EUROPEAN JOURNAL, 2010, 16 (43) :12928-12934

[29] Synthesis and structure of indenylnickel(II) chlorides bearing free N-heterocyclic carbene ligands and their catalysis for styrene polymerization [J].

Xie, Ling-Zhi ;

Sun, Hong-Mei ;

Hu, Dong-Mei ;

Liu, Zhi-Hong ;

Shen, Qi ;

Zhang, Yong .

POLYHEDRON, 2009, 28 (13) :2585-2590

[30] Ruthenium(II) complexes containing PEGylated N-heterocyclic carbene ligands for tunning biocompatibility in the fight against cancer [J].

Barrios, Oscar ;

Inclan, Claudia ;

Herrera, Pablo ;

Bort, Alicia ;

Martin, Avelino ;

Cano, Jesus ;

Diaz-Laviada, Ines ;

Gomez, Rafael .

JOURNAL OF INORGANIC BIOCHEMISTRY, 2025, 262

← 1 2 3 4 5 →