Iminopyridine Manganese and Nickel Complexes: Synthesis, Characterization and Behavior in the Polymerization of 1,3-Butadiene

Giovanni Ricci; Benedetta Palucci; Simona Losio; Anna Sommazzi; Francesco Masi; Guido Pampaloni; Massimo Guelfi

doi:10.1007/s10118-024-3233-2

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Iminopyridine Manganese and Nickel Complexes: Synthesis, Characterization and Behavior in the Polymerization of 1,3-Butadiene

RESEARCH ARTICLE | Updated：2024-12-31

- Iminopyridine Manganese and Nickel Complexes: Synthesis, Characterization and Behavior in the Polymerization of 1,3-Butadiene
- Chinese Journal of Polymer Science Vol. 43, Issue 1, Pages: 83-89(2025)
- Affiliations：
  
  a.CNR-Istituto di Scienze e Tecnologie "Chimiche" "Giulio Natta" (SCITEC), Via A. Corti 12, I-20133 Milano, Italy
  b.Scientific Advisor, Viale Giovanni XXIII 34, I-28100 Novara, Italy
  c.Scientific Advisor, Via Galvani 7, I-26866 Sant’Angelo Lodigiano (LO), Italy
  d.Scientific Advisor, Via E. Fiumalbi 29, I-56025 Pontedera (PI), Italy
  e.Università di Pisa, Dipartimento di Chimica e Chimica Industriale, Via Moruzzi 13, I-56124 Pisa, Italy
  f.Centro per l'Integrazione della Strumentazione Scientifica dell'Università di Pisa (C.I.S.U.P.), Università di Pisa, I-56124 Pisa, Italy
- Author bio：
  
  giovanni.ricci@scitec.cnr.it
- Funds：
- DOI：10.1007/s10118-024-3233-2
  CLC：
- Received：25 July 2024，
  
  Revised：2024-09-04，
  
  Accepted：05 September 2024，
  
  Online First：14 November 2024，
  
  Published：01 January 2025
- Accepted：
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Ricci, G.; Palucci, B.; Losio, S.; Sommazzi, A.; Masi, F.; Pampaloni, G.; Guelfi, M. Iminopyridine manganese and nickel complexes: synthesis, characterization and behavior in the polymerization of 1,3-butadiene. Chinese J. Polym. Sci. 2025, 43, 83–89

Giovanni Ricci, Benedetta Palucci, Simona Losio, et al. Iminopyridine Manganese and Nickel Complexes: Synthesis, Characterization and Behavior in the Polymerization of 1,3-Butadiene[J]. Chinese Journal of Polymer Science, 2025, 43(1): 83-89.
Ricci, G.; Palucci, B.; Losio, S.; Sommazzi, A.; Masi, F.; Pampaloni, G.; Guelfi, M. Iminopyridine manganese and nickel complexes: synthesis, characterization and behavior in the polymerization of 1,3-butadiene. Chinese J. Polym. Sci. 2025, 43, 83–89 DOI： 10.1007/s10118-024-3233-2.

Giovanni Ricci, Benedetta Palucci, Simona Losio, et al. Iminopyridine Manganese and Nickel Complexes: Synthesis, Characterization and Behavior in the Polymerization of 1,3-Butadiene[J]. Chinese Journal of Polymer Science, 2025, 43(1): 83-89. DOI： 10.1007/s10118-024-3233-2.

摘要

Some manganese and nickel pyridyl-imine complexes are synthesized

characterized and used in the polymerization of butadiene

obtaining predominantly 1

2 and exclusively cis-1

4 polymers

respectively.It should be underlined that practically nothing has ever been reported in the literature on manganese-based catalysts for the stereospecific polymerization of conjugated dienes.

Abstract

Some novel manganese and nickel complexes were synthesized by reacting manganese(II) dichloride and nickel(II) dichloride with pyridyl-imine ligands differing in the nature of the substituents at the imino nitrogen atom. All the complexes were characterized by analytical and infrared data: for some of them single crystals were obtained

and their molecular structure was determined by X-ray diffraction. The complexes were used in association with methylaluminoxane (MAO) for the polymerization of 1

3-butadiene obtaining active and selective catalysts giving predominantly 1

2 polybutadiene in case of manganese catalysts and exclusively

cis

-1

4 polybutadiene in case of nickel catalysts.

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references

Porri, L.; A. Giarrusso, A. “Conjugated Diene Polymerization” in Comprehensive Polymer Science , (Eds.: G. Eastmond, A. Edwith, S. Russo, P. Sigwalt) Pergamon Press Ltd., Oxford, 1989, p. 53..

Ricci, G.; Sommazzi, A.; Masi, F.; Ricci, M.; Boglia, A.; Leone, G. Well-defined transition metal complexes with phosphorus and nitrogen ligands for 1,3-dienes polymerization. Coord. Chem. Rev. 2010 , 254 , 661−676..

Ricci, G.; Pampaloni, G.; Sommazzi, A.; Masi, F. Dienes polymerization: where we are and what lies ahead. Macromolecules 2021 , 54 , 5879−5914..

Porri, L.; Giarrusso, A.; Ricci, G. Recent views on the mechanism of diolefin polymerization with transition metal initiator systems. Prog. Polym. Sci. 1991 , 16 , 405−441..

Raynaud, J.; Wu, J.Y.; Ritter, T. Iron-catalyzed polymerization of isoprene and other 1,3-dienes. Angew. Chem. 2012 , 51 , 11805−11808..

Guo, L.; Jing, X.; Xiong, S.; Liu, Y.; Liu, Z.; Chen, C. Influences of Alkyl and Aryl Substituents on Iminopyridine Fe(II)- and Co(II)-Catalyzed Isoprene Polymerization. Polymers 2016 , 8 , 389..

Hashmi, O. H.; Champouret, Y.; Visseaux, M. Highly active iminopyridyl iron-based catalysts for the polymerization of isoprene. Molecules 2019 , 24 , 3024..

Champouret, Y.; Hashmi, O. H.; Visseaux, M. Discrete iron-based complexes: Applications in homogeneous coordination-insertion polymerization catalysis. Coord. Chem. Rev. 2019 , 390 , 127−170..

Ricci, G.; Leone, G.; Zanchin, G.; Palucci, B.; Boccia, A. C.; Sommazzi, A.; Masi, F.; Zacchini, S.; Guelfi, M.; Pampaloni, G. Highly stereoregular 1,3-butadiene and isoprene polymers through monoalkyl- N -aryl-substituted iminopyridine iron complex-based catalysts: synthesis and characterization. Macromolecules 2021 , 54 , 9947−9959..

Zhao, M.; Wang, L.; Mahmood, Q.; Jing, C.; Zhu, G.; Zhang, X.; Wang, X.; Wang, Q. Controlled isoprene polymerization mediated by iminopyridine-iron(II) acetylacetonate pre-catalysts. Appl. Organomet. Chem. 2019 , 33 , e4836..

Scoti, M.; De Stefano, F.; Zanchin, G.; Leone, G.; De Rosa, C.; Ricci, G. Synthesis, structure, and properties of poly(isoprene)s of different constitutions and configurations from catalysts based on complexes of Nd, Co, and Fe. Macromolecules 2023 , 56 , 4629−4638..

Ricci, G.; Boccia, A.C.; Palucci, B.; Sommazzi, A.; Masi, F.; Scoti, M.; De Stefano, F.; De Rosa, C. Synthesis of stereoregular polymyrcenes using neodymium-, iron- and copper-based catalysts. Polym. Chem. 2024 , 15 , 1367−1376..

Ricci, G.; Leone, G.; Zanchin, G.; Masi, F.; Guelfi, M.; Pampaloni, G. Dichloro(2,2′-bipyridine)copper/MAO: an active and stereospecific catalyst for 1,3-diene polymerization. Molecules 2023 , 28 , 374..

Ricci, G.; Leone, G.; Zanchin, G.; Masi, F.; Zacchini, S.; Bresciani, G.; Guelfi, M.; Pampaloni, G. Iminopyridine copper complex-based catalysts for 1,3-dienes stereospecific polymerization. Macromol. Chem. Phys. 2023 , 224 , 2300037..

Boor jr, J. Ziegler polym erization of olefins. X. Transition metal salts having four and more d-electrons. J. Polym. Sci., Part A: Polym. Chem. 1971 , 9 , 3075..

Campora, J.; Ortiz de la Tabla, L.; Palma, P.; Alvarez, E.; Lahoz, F.; Mereiter, K. Synthesis and catalytic activity of cationic allyl complexes of nickel stabilized by a single N-heterocyclic carbene ligand. Organometallics 2006 , 25 , 3314−3316..

Kim, J. S.; Chadran, D.; Park, D. W.; Ha, C. S.; Kim, I. Polymerization of 1,3-butadiene with nickel(II) α -diimine complexes combined with ethylaluminum sesquichloride. Stud. Surf. Sci. Catal. 2007 , 172 , 525−526..

O’Connor, A. R.; White, P. S.; Brookhart, M. The mechanism of polymerization of butadiene by “ligand-free” nickel(II) Complexes. J. Am. Chem. Soc. 2007 , 129 , 4142−4143..

Kim, J. S.; Chandran, D.; Park, D. W.; Ha, C. S.; Kim, I. Polymerization of 1,3-butadiene with nickel(II) α -diimine complexes combined with ethylaluminum sesquichloride. Sci. Technol. Catal . 2006 , 525-526..

O’Connor, A. R.; Brookhart, M. Polymerization of 1,3-dienes and styrene catalyzed by cationic allyl Ni(II) complexes. J. Polym. Sci., Part A: Polym. Chem. 2010 , 48 , 1901−1912..

Singh, A.; Chavda, A.; Nandula, S.; Vir Jasra, R.; Maiti, M. Kinetic study on stereospecific polymerization of 1,3-butadiene using a nickel based catalyst system in environmentally friendly solvent. Ind. Eng. Chem. Res. 2012 , 51 , 11066−11071..

Wang, B.; Gong, D.; Wu, G.; Zhang, X. Polymerization of 1,3-butadiene using (salen)Ni(II) and (salphen)Ni(II) complexes in combination with methyl- aluminoxane. e-Polymers 2012 , 066..

Ai, P.; Chen, L.; Guo, Y.; Jie, S.; Li, B. G. Polymerization of 1,3-butadiene catalyzed by cobalt(II) and nickel(II) complexes bearing imino- or amino-pyridyl alcohol ligands in combination with ethylaluminum sesquichloride. J. Organomet. Chem. 2012 , 705 , 51−58..

Zhang,J.; Gao, W.; Lang, X.; Wu, Q.; Zhang, L.; Mu, Y. Ni(II) and Fe(II) complexes based on bis(imino)aryl pincer ligands: synthesis, structural characterization and catalytic activities. Dalton Trans. 2012 , 41 , 9639−9645..

Nobbs, J. D.; Tomov, A. K.; Cariou, R.; Gibson, V. C.; White, A. J. P.; Britovsek, G. J. P. Thio-Pybox and Thio-Phebox complexes of chromium, iron, cobalt and nickel and their application in ethylene and butadiene polymerisation catalysis. Dalton Trans. 2012 , 41 , 5949−5964..

Vaultier, F.; Monteil, V.; Spitz, R.; Thuilliez, J.; Boisson,C. New insights on Ni-based catalysts for stereospecific polymerization of butadiene. Polym. Chem. 2012 , 3 , 1490−1494..

Liu, H.; Wang, F.; Jia, X. Y.; Liu, L.; Bi, J. F.; Zhang, C. Y.; Zhao, L. P.; Bai, C. X.; Hu, Y. M.; Zhang, X. Q. Synthesis, characterization, and 1,3-butadiene polymerization studies of Co(II), Ni(II), and Fe(II) complexes bearing 2-( N -arylcarboximidoylchloride)quinoline ligand. J. Mol. Catal. A: Chem. 2014 , 391 , 25−35..

Liu, H.; Wang, F.; Han, C.; Zhang, H.; Bai, C.; Hu, Y.; Zhang, X. Cobalt and nickel complexes supported by 2,6-bis(imidate)pyridyl ligands: synthesis, characterization, and 1,3-butadiene polymerization studies. Inorg. Chim. Acta 2015 , 434 , 135−142..

Liu, L.; Wang, F.; Zhang, C.; Liu, H.; Wu, G.; Zhang, X. Thermally robust α-diimine nickel and cobalt complexes for cis -1,4 selective 1,3-butadiene polymerizations. Molecular Catalysis 2022 , 517 , 112044..

Bruker, APEX4 V2021.10-0, Bruker AXS Inc., Madison, Wisconsin, USA, 2021 .

Bruker, SAINT v8.30A, Bruker AXS Inc., Madison, Wisconsin, USA, 2012 .

Bruker, XPREP V2014/2, Bruker AXS Inc., Madison, Wisconsin, USA, 2014 .

Bruker, SADABS V2016/2, Bruker AXS Inc., Madison, Wisconsin, USA, 2016 .

G.M. Sheldrick, SHELXL-2019/1, Bruker AXS Inc., Madison, Wisconsin, USA, 2019 .

Mochel, V. D. C-13 NMR of polybut adiene. J. Polym. Sci., Part A: Polym. Chem. 1972 , 10 , 1009−1018..

Elgert, K. F.; Quack, G.; Stutzel, B. Zur struktur des polybutadiens, 2†. Das 13C-NMR-Spektrum des 1,2-polybutadiens. Makromol. Chem. 1974 , 175 , 1955−1960..

Xu, M.; Wang, Y.; Zhou, Y.; Yao, Z. J. N,N -Chelate nickel(II) complexes bearing Schiff base ligands as efficient hydrogenation catalysts for amine synthesis. J. Organomet. Chem . 2022 , 959 , 122187..

Tsaulwayo, N.; Kumah, R. T.; Ojwach, S. O. Applications of imino-pyridine Ni(II) complexes as catalysts in the transfer hydrogenation of ketones. J. Mol. Struct. 2021 , 1232 , 129987..

Laine, T. V.; Klinga, M.; Leskelä, M. Synthesis and X-ray structures of new mononuclear and dinuclear diimine complexes of late transition metals. Eur. J. Inorg. Chem. 1999 , 6 , 959−964..

Sood, A.; Räisänen, M.; Aitola, E.; Sibaouih, A.; Colacia, E.; Ahlgren, M.; Nieger, M.; Repo, T.; Leskelä, M. Synthesis and cr ystal structure determination of Mn(II) Schiff base complexes and their performance in ethene polymerization. Polyhedron 2013 , 56 , 221−229..

Ban, H.T.; Kase, T.; Murata, M. Manganese-based transition metal complexes as new catalysts for olefin polymerizations. J. Polym. Sci., Part A: Polym. Chem. 2001 , 29 , 3733−3738..

Schulz, M.; Klopfleisch, M.; Görls, H.; Kahnes, M.; Westerhausen, M. Synthesis and structural diversity of 2-pyridylmethylideneamine complexes of zinc(II) chloride. Inorg. Chim. Acta 2009 , 362 , 4706−4712..

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Related Institution

CNR-Istituto di Scienze e Tecnologie "Chimiche" "Giulio Natta" (SCITEC), Via A. Corti 12,- Milano

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Centro per l'Integrazione della Strumentazione Scientifica dell'Università di Pisa (C.I.S.U.P.), Università di Pisa, I

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