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Synthesis, Structure, and Bonding of Linear Sandwich Complexes Of Lanthanidocenes: Synthesis, Structure, and Bonding of Linear Sandwich Complexes of Lanthanides Mathieu Xemard, Sebastien Zimmer, Marie Cordier, Violaine Goudy, Louis Ricard, Carine Clavaguera, Grégory Nocton To cite this version: Mathieu Xemard, Sebastien Zimmer, Marie Cordier, Violaine Goudy, Louis Ricard, et al.. Lan- thanidocenes: Synthesis, Structure, and Bonding of Linear Sandwich Complexes of Lanthanides. Journal of the American Chemical Society, American Chemical Society, 2018, 140 (43), pp.14433- 14439. hal-01999492 HAL Id: hal-01999492 https://hal.archives-ouvertes.fr/hal-01999492 Submitted on 11 Nov 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Lanthanidocenes: Synthesis, Structure and Bonding of Linear Sand- wich Complexes of Lanthanides Mathieu Xémard,† Sébastien Zimmer, † Marie Cordier,† Violaine Goudy,† Louis Ricard, † Carine Clava- guéra,‡ and Grégory Nocton†* † LCM, CNRS, Ecole polytechnique, Université Paris-Saclay, Route de Saclay, 91128 Palaiseau cedex, France. ‡ - - -Saclay, 15 avenue Jean Perrin, 91405 Orsay Cedex, France. ABSTRACT: The article presents the synthesis, structure, and bonding of a series of neutral and linear sandwich compounds with the cyclononatetraenyl (Cnt) ligand and divalent lanthanides. These compounds account for the emergence of the lanthanidocene series in reference to the ferrocene and uranocene. The synthetic strategy uses the solubility difference between two conformation isomers of the ligand as well as their isomerization induced by solvent coordination, yielding to the isomorphous and isostructural, neutral and rigorously linear sandwich complexes. The molecular structures highlight a Cnt-Ln-Cnt angle at 180° and a ring size close to the Cnt-Cnt (centroid) distance. A qualitative molecular orbital diagram is provided in D9d symmetry and DFT calculations enforce the bonding model. INTRODUCTION. For the other lanthanides, three Cp ligands surround the metal 7-8 The initial report of a new type of organo-iron compound in center with +III oxidation states, leading to Cp3Ln, while 1 with +II oxidation states, a bending is induced because of 1951 has marked the onset of an extensive and fruitful re- 18-19 search field devoted to the synthesis and the structural analy- inter-molecular interactions. Furthermore, in Cot chemis- sis of the so-called metallocenes.2-3 The sandwich shape of try, the anionic nature of the trivalent metal complexes also these molecules is fascinating since it provides a great plat- generally results in a bending and/or in the formation of chain form for further substitutions. Additionally, the high sym- structures, preventing the establishment of a systematic isostructural series of linear sandwich complexes of lantha- metry of such molecules is particularly interesting since it 20-22 confers various reactivity and physical properties to the metal nides. center, depending upon the electron count.4 Thus, not only An interesting step toward such a series has been done with that these compounds broke the fundamental nature of the the report of formal zero-valent bis(arene) lanthanides com- structural perspectives of the time, but it also fed multiple pounds synthesized 1980’ with the bulky 1,3,5-tris- research fields for more than 60 years. tert-butylbenzene ligand.23-24 Indeed, in order to reach the The cyclopentadienyl (Cp) ligand (Chart 1) that is used for the desired linear geometry, the preferred solution is to use large substituents, assuming that the sterics will dictate the sym- synthesis of neutral metallocenes is small, Hückel aromatic, 25-27 mono-anionic, and is therefore particularly well adapted for metry. This strategy has proven to be useful in the synthe- 4 + 28 + transition metals of the +II oxidation state. For the main f f c c p’2Ln , w c p’2Dy closely linear geometry allowed to breake records in single group metallocenes, the lone-pair p orbital causes a bending in 29-31 groups 14 and 15 complexes,5-6 while for larger elements with molecule magnets (SMM) properties, but also allowing spontaneous reduction of SmIII32 and extraordinary lumines- different oxidation states, such as the f-elements, the coordi- II 33 nation chemistry studies with the Cp ligand have also led to cence of Eu complexes. other geometries than the linear sandwich one.7-9 Thus, Chart 1. Aromatic ligands used for the design of sandwich com- Streitwieser proposed to use the cyclooctatetraenyl (Cot) plexes. ligand for 5f-elements of +IV oxidation state: in 1968, the synthesis10 and the structure11 of a neutral and linear sandwich complex of uranium was reported and named uranocene, in reference to ferrocene.2-3 For the 4f-elements, the lanthanides, 2- the only element for which the formal +IV oxidation state is well-known is Ce: cerocene, i.e. Ce(Cot)2, is the only one of 12 the series that is reported yet, and the numerous reports on Cp- benzene Cot2- Cnt- its bonding and on the formal oxidation state of cerium13-17 highlight the large fundamental interest for this type of mole- Our strategy is based on the use of divalent lanthanides, 34-35 cules. whose chemistry expended largely in the last decades, with the next Hückel-aromatic and monoanionic ligand after - the Cp ligand, the cyclononatetraenyl anion (Cnt, C9H9 , Chart 36-37 1). A recent article by Nakajima et al. reported the struc- diethylether from a suspension of YbI2 with 2 equivalents of 38 tural and physical properties of the Eu(Cnt)2 complex, while the isomers mixture, the yield remains low (15 %). Perform- Walter et al. have reported the synthesis of the Ba(Cnt)2 com- ing the reaction in thf does not improve the yield since after plex.39 In this article, we report the original synthesis, the evaporation of the solvent and extraction of the residue in structure and the bonding of several Ln(Cnt)2 complexes, a toluene it still remains very similar. However, when the salt series of neutral and linear sandwich compounds of lantha- metathesis reaction is performed directly in toluene with a few nides, justifying the name of lanthanidocenes. drops of thf, the suspension turns immediately green and a good amount (43 %) of the crystals of, Yb(Cnt)2, 1 can be obtained, after filtration, from the green solution at -35 °C. RESULTS AND DISCUSSION. The 1H NMR spectrum shows three different complexes in Synthesis and Structural Analysis. The KCnt salt has been cc 37, 40 solution: the two homoleptic Yb(L1-cis)2, (1 ) Yb(L1-trans)2 prepared from a literature procedure, and can be re- tt ct (1 ) complexes and the heteroleptic Yb(L1-cis)( L1-trans) (1 ) crystallized from diethylether, forming yellow X-ray suitable cc complex (Figure S2). The characteristic singlet of 1 at 7.16 crystals (Figure 1). The structure shows a positional disorder ct tt ppm and both characteristic triplets of 1 and 1 at -3.97 (J = for the C1 carbon atom, indicating the presence of two iso- 15.4 Hz) and -4.13 ppm (J = 15.5 Hz) allow their identifica- mers: the cis,cis,cis,cis-cyclononatetraenyl (L -cis), in which 13 1 tion. The C NMR shows only 6 resonances for the two major all carbon atoms form a regular ring and the cis,cis,cis,trans- cc tt isomers, one for 1 , and 5 for 1 . Among them, 5 resonances cyclononatetraenyl (L1-trans), in which one carbon atom is 1 have JCH coupling constants in a 154-162 Hz range, in good moved inside the ring (Chart 2). 2 agreement with sp aromatic carbon atoms, while the last one 1 3 Chart 2. Structure of the two isomers of L1. has a JCH of 126 Hz, in agreement with an sp carbon atom (Figure S3-S4) and can be attributed to the carbon away from the ring plane. A similar synthetic procedure than that of 1 was used to afford Sm(Cnt)2 (2) in better yields (56 %) as brown crystals (Scheme 1). The 1H NMR shows 12 resonances (three iso- mers) spanning from 50.3 to -2.35 ppm (Figure S8). All of L -cis L -trans 1 1 them can be all identified with a 2D-COSY experiment (Fig- Both isomers are also present in solution (Figure S1): the 1H ure S9). The isomerization must be performed at temperatures NMR spectrum of the crystals in CD3CN shows the character- close to room temperature (25 °C) to be optimum since the istic singlet at 6.94 ppm of L1-cis as well as the characteristic rate of the reaction slows down when increasing the tempera- 37 triplet associated with the internal hydrogen atom (L1-trans) at ture, preventing to realize an Eyring analysis. After several -3.54 ppm in a 1:4 ratio. Boche et al. measured an activation days, the crystallization of yellow (1cc) and orange (2cc) crys- free-enthalpy of 29.7 kcal.mol-1 in thf at 60 °C for the KCnt tals occurs in unsatisfactory low yields,38 which encouraged isomerization process.41 Thus, if the ring opening reaction us to search for better isomerization solvents. time is extended to 3 days instead of several hours, only the Scheme 1. Synthetic scheme for 1, 3 and 4. symmetrical isomer L1-cis is obtained. However, since the latter is not soluble in diethylether, its purification by crystal- lization is rendered very difficult. When crystals of 1 are dissolved in thf, red crystals crashed out immediately while the dilute 1H NMR shows only one Figure 1.
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