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SYNTHESIS OF NOVEL BIS(PHOSPHINO)AMINE-RUII(ACAC)2 COMPLEXES, AND INVESTIGATION OF CATALYTIC ACTIVITY IN TRANSFER HYDROGENATION

Year 2022, Volume: 8 Issue: 2, 147 - 156, 31.12.2022

Duygu Elma Karakaş Uğur Işık Murat Aydemir Feyyaz Durap Akın Baysal

https://doi.org/10.51477/mejs.1180235

Abstract

In this study, reactions of (PPh2)2NCH2CH2N(PPh2)2 (L1) and {(PPh2)2NCH2CH2}3N (L2) with [RuII(acac)2(CH3CN)2] led to the production of new dinuclear complex [Ru(acac)2]2(L1) (1) and trinuclear complex [Ru(acac)2]3(L2) (2). Complex 1 and 2 are excellent candidates for the role of catalyst precursors in the transfer hydrogenation (TH) of acetophenone and its derivatives. Compared to complex (1), the trinuclear complex (2) is an exceptional catalyst, producing the corresponding alcohols in 98–99% yields in 20 minutes at 80 oC (TOF≤300 h-1) for the TH process. A comparison of the catalytic properties of the complexes is also briefly discussed. Complex structures have also been characterized by combining nuclear magnetic resonance (NMR), Fourier transform infrared (FT-IR), and elemental analysis.

Keywords

Transfer Hydrogenation Ruthenium Complex Homogeneous Catalysis. Aminophosphine

Supporting Institution

Siirt University

Project Number

2017-SIULAB-48

Thanks

Financial support from Siirt University Research Fund (Project number: 2017-SIULAB-48) is gratefully acknowledged.

References

  • [1] Aydemir M, Baysal A, Turgut Y. Applications of transition metal complexes containing aminophosphine ligand to transfer hydrogenation of ketones. Applied Organometallic Chemistry. 2011;25:270-5.
  • [2] Li F, France LJ, Cai Z, Li Y, Liu S, Lou H, et al. Catalytic transfer hydrogenation of butyl levulinate to γ-valerolactone over zirconium phosphates with adjustable Lewis and Brønsted acid sites. Applied Catalysis B: Environmental. 2017;214:67-77.
  • [3] Wang D, Astruc D. The golden age of transfer hydrogenation. Chemical reviews. 2015;115:6621-86.
  • [4] Gilkey MJ, Vlachos DG, Xu B. Poisoning of Ru/C by homogeneous Brønsted acids in hydrodeoxygenation of 2, 5-dimethylfuran via catalytic transfer hydrogenation. Applied Catalysis A: General. 2017;542:327-35.
  • [5] Gnanamgari D, Sauer EL, Schley ND, Butler C, Incarvito CD, Crabtree RH. Iridium and ruthenium complexes with chelating N-heterocyclic carbenes: efficient catalysts for transfer hydrogenation, β-alkylation of alcohols, and N-alkylation of amines. Organometallics. 2009;28:321-5.
  • [6] Yiǧit M, Yiǧit B, Özdemir İ, Çetinkaya E, Çetinkaya B. Active ruthenium‐(N‐heterocyclic carbene) complexes for hydrogenation of ketones. Applied organometallic chemistry. 2006;20:322-7.
  • [7] Elma D, Durap F, Aydemir M, Baysal A, Meric N, Ak B, et al. Screening of C2-symmetric chiral phosphinites as ligands for ruthenium (II)-catalyzed asymmetric transfer hydrogenation of prochiral aromatic ketones. Journal of Organometallic Chemistry. 2013;729:46-52.
  • [8] Chang Y-C, Hu C-Y, Liang Y-H, Hong F-E. Computational and 31P NMR studies of moisture-metastable cyclic diaminophosphine oxide preligands. Polyhedron. 2016;105:123-36.
  • [9] Gholivand K, Kahnouji M, Maghsoud Y, Hosseini M, Roe SM. Synthesis, structure, computational and catalytic activities of palladium complexes containing hydrazide based amino-phosphine ligands. Journal of Organometallic Chemistry. 2019;880:281-92.
  • [10] Biricik N, Durap F, Gümgüm B, Fei Z, Scopelliti R. Synthesis and reactivity of N, N-bis (diphenylphosphino) dimethylaniline compounds. Transition Metal Chemistry. 2007;32:877-83.
  • [11] Aydemir M, Baysal A, Durap F, Gümgüm B, Özkar S, Yıldırım LT. Synthesis and characterization of transition metal complexes of thiophene‐2‐methylamine: X‐ray crystal structure of palladium (II) and platinum (II) complexes and use of palladium (II) complexes as pre‐catalyst in Heck and Suzuki cross‐coupling reactions. Applied Organometallic Chemistry. 2009;23:467-75.
  • [12] Kaur N. Copper catalysts in the synthesis of five-membered N-polyheterocycles. Current Organic Synthesis. 2018;15:940-71.
  • [13] Sushev VV, Kornev AN, Min’ko YA, Belina NV, Kurskiy YA, Kuznetsova OV, et al. Rearrangement of phosphinohydrazide ligand–NPh-N (PPh2) 2 in transition metal coordination sphere: Synthesis and characterization of nickel and cobalt spirocyclic complexes M (NPh-PPh2N-PPh2) 2 and their properties. Journal of organometallic chemistry. 2006;691:879-89.
  • [14] Fedotova YV, Kornev AN, Sushev VV, Kursky YA, Mushtina TG, Makarenko NP, et al. Phosphinohydrazines and phosphinohydrazides M (–N (R)–N (R)–PPh2) n of some transition and main group metals: synthesis and characterization: Rearrangement of Ph2P–NR–NR–ligands into aminoiminophosphorane, RNPPh2–NR–, and related chemistry. Journal of organometallic chemistry. 2004;689:3060-74.
  • [15] Sarcher C, Lebedkin S, Kappes MM, Fuhr O, Roesky PW. Bi-and tetrametallic complexes of the noble metals with PNP-ligands. Journal of Organometallic Chemistry. 2014;751:343-50.
  • [16] Naktode K, Kottalanka RK, Adimulam H, Panda TK. Tetra-nuclear copper complex having P–N–P ligand to P–O–P ligand–synthesis, structural, and mechanistic studies. Journal of Coordination Chemistry. 2014;67:3042-53.
  • [17] Kama DV, Brink A, Visser HG. Crystal structure of bis (μ2-chlorido)-bis (di-p-tolylhydroxyphosphine-κP)-bis (di-p-tolylphosphite-κP) dipalladium (II), C56H58Cl2O4P4Pd2. Zeitschrift für Kristallographie-New Crystal Structures. 2016;231:1081-3.
  • [18] Kornev AN, Sushev VV, Panova YS, Belina NV, Lukoyanova OV, Fukin GK, et al. The Intramolecular Rearrangement of Phosphinohydrazides [R′ 2P–NR–NR–M]→[RN PR′ 2–NR–M]: General Rules and Exceptions. Transformations of Bulky Phosphinohydrazines (R–NH–N (PPh2) 2, R= t Bu, Ph2P). Inorganic Chemistry. 2012;51:874-81.
  • [19] Ok F, Aydemir M, Durap F, Baysal A. Novel half‐sandwich η5‐Cp*–rhodium (III) and η5‐Cp*–ruthenium (II) complexes bearing bis (phosphino) amine ligands and their use in the transfer hydrogenation of aromatic ketones. Applied Organometallic Chemistry. 2014;28:38-43.
  • [20] Oomura K-i, Ooyama D, Satoh Y, Nagao N, Nagao H, Howell FS, et al. Redox behavior of a binuclear ruthenium complex having a di-μ-nitrosyl ligand,[Ru (acac) 22 (μ-NO) 2](acac= acetylacetonato). Inorganica chimica acta. 1998;269:342-6.
  • [21] Akba O, Durap F, Aydemir M, Baysal A, Gümgüm B, Özkar S. Synthesis and characterizations of N, N, N′, N′-tetrakis (diphenylphosphino) ethylendiamine derivatives: Use of palladium (II) complex as pre-catalyst in Suzuki coupling and Heck reactions. Journal of Organometallic Chemistry. 2009;694:731-6.
  • [22] Gümgüm B, Akba O, Durap F, Yıldırım LT, Ülkü D, Özkar S. Synthesis, characterization, crystal and molecular structure of diphenyloxophosphinoethylenediamines. Polyhedron. 2006;25:3133-7.
  • [23] Aydemir M, Baysal A, Gümgüm B. Synthesis and characterization of tris {2-(N, N-bis (diphenylphosphino) aminoethyl} amine derivatives: Application of a palladium (II) complex as a pre-catalyst in the Heck and Suzuki cross-coupling reactions. Journal of Organometallic Chemistry. 2008;693:3810-4.
  • [24] Tokgun O, Karakas DE, Tan S, Karagür ER, İnal B, Akca H, et al. Novel ruthenium and palladium complexes as potential anticancer molecules on SCLC and NSCLC cell lines. Chemical Papers. 2020;74:2883-92.
  • [25] Mannu A, Grabulosa A, Baldino S. Transfer Hydrogenation from 2-propanol to Acetophenone Catalyzed by [RuCl2 (η6-arene) P](P= monophosphine) and [Rh (PP) 2] X (PP= diphosphine, X= Cl−, BF4−) Complexes. Catalysts. 2020;10:162.
  • [26] Ak B, Elma D, Meriç N, Kayan C, Işık U, Aydemir M, et al. New chiral ruthenium (II)–phosphinite complexes containing a ferrocenyl group in enantioselective transfer hydrogenations of aromatic ketones. Tetrahedron: Asymmetry. 2013;24:1257-64.
  • [27] Kayan C, Meriç N, Rafikova K, Zazybin A, Gürbüz N, Karakaplan M, et al. A new class of well-defined ruthenium catalysts for enantioselective transfer hydrogenation of various ketones. Journal of Organometallic Chemistry. 2018;869:37-47.
  • [28] Ak B, Aydemir M, Durap F, Meriç N, Elma D, Baysal A. Highly efficient iridium catalysts based on C2-symmetric ferrocenyl phosphinite ligands for asymmetric transfer hydrogenations of aromatic ketones. Tetrahedron: Asymmetry. 2015;26:1307-13.
  • [29] Uğur I, MERİÇ N, AYDEMİR M. NOVEL MONONUCLEAR METAL-PHOSPHINITE COMPOUNDS AND CATALYTIC PERFORMANCE IN TRANSFER HYDROGENATION OF KETONES. Middle East Journal of Science.8:1-15.
  • [30] Faller J, Lavoie AR. Catalysts for the asymmetric transfer hydrogenation of ketones derived from L-prolinamide and (p-cymeneRuCl2) 2 or (Cp* RhCl2) 2. Organometallics. 2001;20:5245-7.
  • [31] Ödemir I, Yaşar S, Çetinkaya B. Ruthenium (II) N-heterocyclic carbene complexes in the transfer hydrogenation of ketones. Transition metal chemistry. 2005;30:831-5.

Year 2022, Volume: 8 Issue: 2, 147 - 156, 31.12.2022

Duygu Elma Karakaş Uğur Işık Murat Aydemir Feyyaz Durap Akın Baysal

https://doi.org/10.51477/mejs.1180235

Abstract

Project Number

2017-SIULAB-48

References

  • [1] Aydemir M, Baysal A, Turgut Y. Applications of transition metal complexes containing aminophosphine ligand to transfer hydrogenation of ketones. Applied Organometallic Chemistry. 2011;25:270-5.
  • [2] Li F, France LJ, Cai Z, Li Y, Liu S, Lou H, et al. Catalytic transfer hydrogenation of butyl levulinate to γ-valerolactone over zirconium phosphates with adjustable Lewis and Brønsted acid sites. Applied Catalysis B: Environmental. 2017;214:67-77.
  • [3] Wang D, Astruc D. The golden age of transfer hydrogenation. Chemical reviews. 2015;115:6621-86.
  • [4] Gilkey MJ, Vlachos DG, Xu B. Poisoning of Ru/C by homogeneous Brønsted acids in hydrodeoxygenation of 2, 5-dimethylfuran via catalytic transfer hydrogenation. Applied Catalysis A: General. 2017;542:327-35.
  • [5] Gnanamgari D, Sauer EL, Schley ND, Butler C, Incarvito CD, Crabtree RH. Iridium and ruthenium complexes with chelating N-heterocyclic carbenes: efficient catalysts for transfer hydrogenation, β-alkylation of alcohols, and N-alkylation of amines. Organometallics. 2009;28:321-5.
  • [6] Yiǧit M, Yiǧit B, Özdemir İ, Çetinkaya E, Çetinkaya B. Active ruthenium‐(N‐heterocyclic carbene) complexes for hydrogenation of ketones. Applied organometallic chemistry. 2006;20:322-7.
  • [7] Elma D, Durap F, Aydemir M, Baysal A, Meric N, Ak B, et al. Screening of C2-symmetric chiral phosphinites as ligands for ruthenium (II)-catalyzed asymmetric transfer hydrogenation of prochiral aromatic ketones. Journal of Organometallic Chemistry. 2013;729:46-52.
  • [8] Chang Y-C, Hu C-Y, Liang Y-H, Hong F-E. Computational and 31P NMR studies of moisture-metastable cyclic diaminophosphine oxide preligands. Polyhedron. 2016;105:123-36.
  • [9] Gholivand K, Kahnouji M, Maghsoud Y, Hosseini M, Roe SM. Synthesis, structure, computational and catalytic activities of palladium complexes containing hydrazide based amino-phosphine ligands. Journal of Organometallic Chemistry. 2019;880:281-92.
  • [10] Biricik N, Durap F, Gümgüm B, Fei Z, Scopelliti R. Synthesis and reactivity of N, N-bis (diphenylphosphino) dimethylaniline compounds. Transition Metal Chemistry. 2007;32:877-83.
  • [11] Aydemir M, Baysal A, Durap F, Gümgüm B, Özkar S, Yıldırım LT. Synthesis and characterization of transition metal complexes of thiophene‐2‐methylamine: X‐ray crystal structure of palladium (II) and platinum (II) complexes and use of palladium (II) complexes as pre‐catalyst in Heck and Suzuki cross‐coupling reactions. Applied Organometallic Chemistry. 2009;23:467-75.
  • [12] Kaur N. Copper catalysts in the synthesis of five-membered N-polyheterocycles. Current Organic Synthesis. 2018;15:940-71.
  • [13] Sushev VV, Kornev AN, Min’ko YA, Belina NV, Kurskiy YA, Kuznetsova OV, et al. Rearrangement of phosphinohydrazide ligand–NPh-N (PPh2) 2 in transition metal coordination sphere: Synthesis and characterization of nickel and cobalt spirocyclic complexes M (NPh-PPh2N-PPh2) 2 and their properties. Journal of organometallic chemistry. 2006;691:879-89.
  • [14] Fedotova YV, Kornev AN, Sushev VV, Kursky YA, Mushtina TG, Makarenko NP, et al. Phosphinohydrazines and phosphinohydrazides M (–N (R)–N (R)–PPh2) n of some transition and main group metals: synthesis and characterization: Rearrangement of Ph2P–NR–NR–ligands into aminoiminophosphorane, RNPPh2–NR–, and related chemistry. Journal of organometallic chemistry. 2004;689:3060-74.
  • [15] Sarcher C, Lebedkin S, Kappes MM, Fuhr O, Roesky PW. Bi-and tetrametallic complexes of the noble metals with PNP-ligands. Journal of Organometallic Chemistry. 2014;751:343-50.
  • [16] Naktode K, Kottalanka RK, Adimulam H, Panda TK. Tetra-nuclear copper complex having P–N–P ligand to P–O–P ligand–synthesis, structural, and mechanistic studies. Journal of Coordination Chemistry. 2014;67:3042-53.
  • [17] Kama DV, Brink A, Visser HG. Crystal structure of bis (μ2-chlorido)-bis (di-p-tolylhydroxyphosphine-κP)-bis (di-p-tolylphosphite-κP) dipalladium (II), C56H58Cl2O4P4Pd2. Zeitschrift für Kristallographie-New Crystal Structures. 2016;231:1081-3.
  • [18] Kornev AN, Sushev VV, Panova YS, Belina NV, Lukoyanova OV, Fukin GK, et al. The Intramolecular Rearrangement of Phosphinohydrazides [R′ 2P–NR–NR–M]→[RN PR′ 2–NR–M]: General Rules and Exceptions. Transformations of Bulky Phosphinohydrazines (R–NH–N (PPh2) 2, R= t Bu, Ph2P). Inorganic Chemistry. 2012;51:874-81.
  • [19] Ok F, Aydemir M, Durap F, Baysal A. Novel half‐sandwich η5‐Cp*–rhodium (III) and η5‐Cp*–ruthenium (II) complexes bearing bis (phosphino) amine ligands and their use in the transfer hydrogenation of aromatic ketones. Applied Organometallic Chemistry. 2014;28:38-43.
  • [20] Oomura K-i, Ooyama D, Satoh Y, Nagao N, Nagao H, Howell FS, et al. Redox behavior of a binuclear ruthenium complex having a di-μ-nitrosyl ligand,[Ru (acac) 22 (μ-NO) 2](acac= acetylacetonato). Inorganica chimica acta. 1998;269:342-6.
  • [21] Akba O, Durap F, Aydemir M, Baysal A, Gümgüm B, Özkar S. Synthesis and characterizations of N, N, N′, N′-tetrakis (diphenylphosphino) ethylendiamine derivatives: Use of palladium (II) complex as pre-catalyst in Suzuki coupling and Heck reactions. Journal of Organometallic Chemistry. 2009;694:731-6.
  • [22] Gümgüm B, Akba O, Durap F, Yıldırım LT, Ülkü D, Özkar S. Synthesis, characterization, crystal and molecular structure of diphenyloxophosphinoethylenediamines. Polyhedron. 2006;25:3133-7.
  • [23] Aydemir M, Baysal A, Gümgüm B. Synthesis and characterization of tris {2-(N, N-bis (diphenylphosphino) aminoethyl} amine derivatives: Application of a palladium (II) complex as a pre-catalyst in the Heck and Suzuki cross-coupling reactions. Journal of Organometallic Chemistry. 2008;693:3810-4.
  • [24] Tokgun O, Karakas DE, Tan S, Karagür ER, İnal B, Akca H, et al. Novel ruthenium and palladium complexes as potential anticancer molecules on SCLC and NSCLC cell lines. Chemical Papers. 2020;74:2883-92.
  • [25] Mannu A, Grabulosa A, Baldino S. Transfer Hydrogenation from 2-propanol to Acetophenone Catalyzed by [RuCl2 (η6-arene) P](P= monophosphine) and [Rh (PP) 2] X (PP= diphosphine, X= Cl−, BF4−) Complexes. Catalysts. 2020;10:162.
  • [26] Ak B, Elma D, Meriç N, Kayan C, Işık U, Aydemir M, et al. New chiral ruthenium (II)–phosphinite complexes containing a ferrocenyl group in enantioselective transfer hydrogenations of aromatic ketones. Tetrahedron: Asymmetry. 2013;24:1257-64.
  • [27] Kayan C, Meriç N, Rafikova K, Zazybin A, Gürbüz N, Karakaplan M, et al. A new class of well-defined ruthenium catalysts for enantioselective transfer hydrogenation of various ketones. Journal of Organometallic Chemistry. 2018;869:37-47.
  • [28] Ak B, Aydemir M, Durap F, Meriç N, Elma D, Baysal A. Highly efficient iridium catalysts based on C2-symmetric ferrocenyl phosphinite ligands for asymmetric transfer hydrogenations of aromatic ketones. Tetrahedron: Asymmetry. 2015;26:1307-13.
  • [29] Uğur I, MERİÇ N, AYDEMİR M. NOVEL MONONUCLEAR METAL-PHOSPHINITE COMPOUNDS AND CATALYTIC PERFORMANCE IN TRANSFER HYDROGENATION OF KETONES. Middle East Journal of Science.8:1-15.
  • [30] Faller J, Lavoie AR. Catalysts for the asymmetric transfer hydrogenation of ketones derived from L-prolinamide and (p-cymeneRuCl2) 2 or (Cp* RhCl2) 2. Organometallics. 2001;20:5245-7.
  • [31] Ödemir I, Yaşar S, Çetinkaya B. Ruthenium (II) N-heterocyclic carbene complexes in the transfer hydrogenation of ketones. Transition metal chemistry. 2005;30:831-5.
There are 31 citations in total.

Details

Primary Language English
Subjects Inorganic Chemistry
Journal Section Article
Authors

Duygu Elma Karakaş 0000-0003-2582-9993

Uğur Işık 0000-0003-1010-9563

Murat Aydemir 0000-0002-4238-5012

Feyyaz Durap 0000-0003-0899-1948

Akın Baysal 0000-0001-7294-6792

Project Number 2017-SIULAB-48
Publication Date December 31, 2022
Submission Date September 26, 2022
Acceptance Date December 31, 2022
Published in Issue Year 2022 Volume: 8 Issue: 2

Cite

IEEE D. Elma Karakaş, U. Işık, M. Aydemir, F. Durap, and A. Baysal, “SYNTHESIS OF NOVEL BIS(PHOSPHINO)AMINE-RUII(ACAC)2 COMPLEXES, AND INVESTIGATION OF CATALYTIC ACTIVITY IN TRANSFER HYDROGENATION”, MEJS, vol. 8, no. 2, pp. 147–156, 2022, doi: 10.51477/mejs.1180235.
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