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Amidation of Aldehydes Using Mono-Cationic Half-Sandwich Rhodium(III) Complexes with Functionalized Phenylhydrazone Ligands

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Amidation of Aldehydes Using Mono-Cationic Half-Sandwich Rhodium(III) Complexes with Functionalized Phenylhydrazone Ligands Journal of Organometallic Chemistry 886 (2019) 65e70 Contents lists available at ScienceDirect Journal of Organometallic Chemistry journal homepage: www.elsevier.com/locate/jorganchem Amidation of aldehydes using mono-cationic half-sandwich rhodium(III) complexes with functionalized phenylhydrazone ligands Neelakandan Devika a, b, Subbiah Ananthalakshmi c, Nandhagopal Raja a, d, * Gajendra Gupta a, Bruno Therrien a, a Institute of Chemistry, University of Neuchatel, Avenue de Bellevaux 51, CH-2000, Neuchatel, Switzerland b Department of Chemistry, BIT campus, Anna University, Tiruchirappalli, 620 024, India c Department of Chemistry, Urumu Dhanalakshmi College, Tiruchirappalli, 620 019, India d Department of Chemistry, University College of Engineering, Anna University, Ariyalur, 621 704, India article info abstract Article history: A series of mono-cationic half-sandwich rhodium(III) complexes have been synthesized in methanol Received 22 November 2018 5 using phenylhydrazone-derived ligands (L1eL6) and the starting precursor [(h -C5Me5)2Rh2(m-Cl)2Cl2]in Received in revised form a 2:1 molar ratio. The N,N0-phenylhydrazone complexes have been isolated as tetraphenylborate salts. All 21 February 2019 complexes were characterized by elemental analysis, FT-IR, UVevisible, NMR spectroscopy and mass Accepted 21 February 2019 5 spectrometry. The molecular structure of complex [(h -C5Me5)Rh(L1)Cl](BPh4)(1) was confirmed by Available online 26 February 2019 5 single-crystal X-ray structure analysis. Complex [(h -C5Me5)Rh(L3)Cl](BPh4)(3) was used as an efficient catalyst for the amide formation reaction, with up to 99% conversion after 2 h in toluene at 110 C in the Keywords: Phenylhydrazone-based ligands presence of hydroxyl amine hydrochloride and sodium bicarbonate. © Half-sandwich complexes 2019 Elsevier B.V. All rights reserved. Homogenous catalysis Pentamethylcyclopentadienyl rhodium complexes Amidation reaction 1. Introduction functional diversity. The structural properties of the hydrazone group enable its use in various applications [13]. Furthermore, Organometallic compounds are powerful catalytic agents in chemical functionalization of the hydrazone group can increase its synthetic organic chemistry [1]. Rhodium based complexes are very stability, modify its coordination ability, and generate higher important for different catalytic reactions like the transfer hydro- modularity, thus overall fine-tuning the steric and electronic genation [2], hydroformylation [3], hydrosilylation [4], coupling properties of the resulting complex for optimization of the catalytic reactions [5], ring opening [6], ring closing [7], polymerisation [8], process [14]. oxidation [9], isomerization [10], and others. Both oxidative addi- The amide bond is present in many natural and synthetic tion and reductive elimination reactions are readily accessible, and polymers, as well as in peptides and proteins [15]. Amide bonds are accordingly, rhodium complexes have been widely used in the typically synthesized by acylation of amines with carboxylic acid design of catalytic systems [11]. derivatives such as acid chloride, anhydride, active esters, etc … In parallel, ligand design is vital for the development of catalysts However, these methods have the inconvenience of producing a [12]. The structure of the ligand dictates the environment of the stoichiometric amount of side products and of using highly haz- metal centers and subsequently the catalytic activity. Hydrazone- ardous reagents [16]. Therefore, alternative methods for amide derived ligands possess distinct features that make them inter- synthesis have been developed, such as the Beckmann rearrange- esting for the design of metal-based catalysts. The tri-atomic ment [17], the Staudinger reaction [18], the Schmidt reaction [19], C¼NeN structure of hydrazone introduces electrophilic and the amino carbonylation of halo arenes [20], the iodonium- nucleophilic characters to the ligand, which also offers great promoted alkyl halo nitro alkane amine coupling [21], the direct amide synthesis from alcohols with amines or nitroarenes [22,23], the hydro amination of alkynes [24], the amidation of thioacids * Corresponding author. with azides [25], as well as the trans-amidation of primary amides E-mail address: [email protected] (B. Therrien). https://doi.org/10.1016/j.jorganchem.2019.02.018 0022-328X/© 2019 Elsevier B.V. All rights reserved. 66 N. Devika et al. / Journal of Organometallic Chemistry 886 (2019) 65e70 [26]. An elegant alternative pathway, which is more atom economic 390 nm, which is assigned to MLCT transitions, and a band around and makes use of cheap and abundant starting materials, is the 290e230 nm, which is attributed to n-p*orp-p* transitions. 1 oxidative amidation of aldehyde with amines [27], using metal- H NMR spectra were recorded in CD3CN, and they confirm the based catalysts [28e37]. These catalytic reactions require large proposed structure of the complexes. The aromatic protons of the amount of catalysts and are generally performed at high temper- complexes appear as one doublet of triplet and one triplet of ature [38e40]. doublet in the range of 8.82e8.79 ppm and 8.20e8.03 ppm, while In contrast to the considerable growth of literature on the the remaining aromatic protons appeared as a multiplet in the chemistry of hydrazone complexes, to the best of our knowledge, range of 8.03e7.08 ppm. The protons of the tetraphenyl borate there are no reports available concerning the catalytic trans- counter ion appear as a multiplet (~7.30 ppm) and two triplets at formation of aldehyde to amides by half-sandwich rhodium(III) ~7.03 and ~6.88 ppm, respectively. The complexes show a broad phenylhydrazone complexes containing N,N0-hydrazine-based do- singlet in the range of 9.21e8.94 ppm corresponding to the unco- nors. In view of the interest to understand the behavior of these ordinated NH proton. The acetyl methyl proton of complexes 1, 2 simple and inexpensive ligands towards rhodium, six half- and 3 appears as a sharp singlet at 2.60 ppm. Finally, the methyl sandwich rhodium metal complexes containing hydrazine- protons of the pentamethylcyclopentadienyl ring (Cp*) are derived ligands were synthesized. All complexes were fully char- observed as a sharp singlet at ~1.47 ppm. The electrospray ioniza- acterized by spectroscopic and spectrometric methods, and one tion mass spectra of 1e6 display a molecular ion peak, which cor- complex was tested as catalyst for the conversion of aldehydes to responds, after the loss of the BPh4 counter anion, to the cationic 5 þ amides in the presence of NH2OH∙HCl and NaHCO3. complexes [(h -C5Me5)Rh(L)Cl] . The molecular structure of 1 was unambiguously confirmed by single-crystal X-ray structure analysis. The ortep diagram of the 2. Results and discussion 5 þ mono-cationic complex [(h -C5Me5)Rh(L1)Cl] is presented in Six half-sandwich rhodium(III) complexes have been synthe- Fig. S1, together with selected bond lengths and angles. The com- 5 plex is chiral, but crystallizes in the centrosymmetric space group sized from the rhodium starting precursor [(h -C5Me5)2Rh2(m- P À1, thus displaying in the crystal both enantiomers. The complex Cl)2Cl2], the phenyl hydrazone ligands (L1eL6) and sodium tetra- phenylborate in a 1:2:2 molar ratio in dry methanol under reflux shows a typical pseudo-tetrahedral geometry (piano-stool) around the metal center with an h5-coordinated Cp*, a chloride, and the for 6 h (Scheme 1). The complexes were isolated as tetraphe- 0 nylborate salts. All complexes are air-stable, non-hygroscopic in N,N -hydrazone ligand (L1). The bond length between the rhodium nature, partially soluble in water and highly soluble in common and the chloride is 2.4160(6) Å, while the two Rh-N bond lengths solvents such as chloroform, dichloromethane, acetonitrile and are almost identical at 2.099(2) Å (Rh-Npyridyl) and 2.101(2) Å (Rh- dimethyl sulfoxide. The complexes were found to be diamagnetic, Nimine). Upon coordination, the phenyl group of the hydrazine À low spin in nature and characterized by elemental analysis, ligand is out of the pyridyl-azomethine plane by 69.3(3) . e 1 13 Overall, these geometrical parameters are consistent with those infrared, UV visible, H NMR, C NMR spectroscopy and ESI mass 0 spectrometry (see experimental part). found in analogous N,N -coordinated rhodium pentam- The coordination mode of the phenylhydrazone ligand to the ethylcyclopentadienyl compounds [41]. rhodium metal center was first investigated by infrared spectros- In the crystal packing of 1, two mono-cationic complexes are copy. The spectra of the ligands were compared to those of the facing each other, thus forming dimers in the solid state. In these corresponding half-sandwich rhodium complexes. The phenyl- dimers (Fig. S2), strong hydrogen bonds are observed, involving / / hydrazone ligands showed a very strong absorption around both the N-H and the chloride. The N-H Cl contact shows a N Cl À / 1600e1620 cm 1, corresponding to the azomethine (C¼N) group. distance of 3.328(2) Å, with a N-H Cl angle of 157(2) , while the C- / / After coordination, the azomethine frequency is shifted to lower H Cl contact possesses a C Cl distance of 3.642(3) Å and a C- À / frequency at around 1565e1600 cm 1. This is due to the reduction H Cl angle of 141 . The separation between the two cationic / of the electron density upon coordination of the azomethine group. complexes is only 6.2120(8) Å (Rh Rh distance). Thus the infrared data confirmed the coordination of the
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