Structure and bonding patterns in heterometallic organometallics with linear Ln-Pd-Ln motifs.

Complexes with short intermetallic distances between transition metal fragments and lanthanide (Ln) fragments are fascinating objects of study, owing to the ambiguity of the nature of the interaction. The addition of the divalent lanthanide fragments Cp*2Ln(OEt2) (Ln = Sm or Yb) to a Pd(ii) complex bearing the deprotonated form of the redox-active, non-symmetrical ligand, 2-pyrimidin-2-yl-1H-benzimidazole (Hbimpm), leads to two isostructural complexes, of the general formula (Cp*2Ln)2[µ-Pd(pyridyl)2] (Ln = Sm (4) and Yb (5)). These adducts have interesting features, such as unique linear Ln-Pd-Ln arrangements and short Ln-Pd distances, which deviate from the expected lanthanide contraction. A mixed computational and spectroscopic study into the formation of these adducts gathers important clues as to their formation. At the same time, thorough characterization of these complexes establishes the +3 oxidation state of all the involved Ln centers. Detailed theoretical computations demonstrate that the apparent deviation from lanthanide contraction is not due to any difference in the intermetallic interaction between the Pd and the Ln, but that the fragments are joined together by electrostatic interactions and dispersive forces. This conclusion contrasts with the findings about a third complex, Cp*2Yb(µ-Me)2PdCp* (6), formed during the reaction, which also possesses a short Yb-Pd distance. Studies at the CASSCF level of theory on this complex show several orbitals containing significant interactions between the 4f and 4d manifolds of the metals. This demonstrates the need for methodical and careful analyses in gauging the intermetallic interaction and the inadequacy of empirical metrics in describing such phenomena.

Molecular Lanthanide Switches for Magnetism and Photoluminescence.

Solvation of [(CNT)Ln(η8 -COT)] (Ln=La, Ce, Nd, Tb, Er; CNT=cyclononatetraenyl, i.e., C9 H9 - ; COT=cyclooctatetraendiid, i.e., C8 H8 2- ) complexes with tetrahydrofuran (THF) gives rise to neutral [(η4 -CNT)Ln(thf)2 (η8 -COT)] (Ln=La, Ce) and ionic [Ln(thf)x (η8 -COT)][CNT] (x=4 (Ce, Nd, Tb), 3 (Er)) species in a solid-to-solid transformation. Due to the severe distortion of the ligand sphere upon solvation, these species act as switchable luminophores and single-molecule magnets. The desolvation of the coordinated solvents can be triggered by applying a dynamic vacuum, as well as a temperature gradient stimulus. Raman spectroscopic investigations revealed fast and fully reversible solvation and desolvation processes. Moreover, we also show that a Nd:YAG laser can induce the necessary temperature gradient for a self-sufficient switching process of the Ce(III) analogue in a spatially resolved manner.

Size-Controlled Hapticity Switching in [Ln(C9 H9 )(C8 H8 )] Sandwiches.

Sandwich complexes of lanthanides have recently attracted a considerable amount of interest due to their applications as Single Molecule Magnet (SMM). Herein, a comprehensive series of heteroleptic lanthanide sandwich complexes ligated by the cyclononatetraenyl (Cnt) and the cyclooctatetraenyl (Cot) ligand [Ln(Cot)(Cnt)] (Ln=Tb, Dy, Er, Ho, Yb, and Lu) is reported. The coordination behavior of the Cnt ligand has been investigated along the series and shows different coordination patterns in the solid-state depending on the size of the corresponding lanthanide ion without altering its overall anisotropy. Besides the characterization in the solid state by single-crystal X-ray diffraction and in solution by 1 H NMR, static magnetic studies and ab initio computational studies were performed.

Synthesis of CF3-Containing Spirocyclic Indolines via a Red-Light-Mediated Trifluoromethylation/Dearomatization Cascade.

A red-light-mediated nPr-DMQA+-catalyzed cascade intramolecular trifluoromethylation and dearomatization of indole derivatives with Umemoto's reagent has been developed. This protocol provides a facile and efficient approach for the construction of functionalized and potentially biologically important CF3-containing 3,3-spirocyclic indolines with moderate to high yields and excellent diastereoselectivities under mild conditions. The success of multiple gram-scale (1 and 10 g) experiments further highlights the robustness and practicality of this protocol and the merit of the employment of red light. Mechanistic studies support the formation of a crucial CF3 radical species and a dearomatized benzyl carbocation intermediate.

Trioxatriangulenium (TOTA+) as a robust carbon-based Lewis acid in frustrated Lewis pair chemistry.

We report the reactivity between the water stable Lewis acidic trioxatriangulenium ion (TOTA+) and a series of Lewis bases such as phosphines and N-heterocyclic carbene (NHC). The nature of the Lewis acid-base interaction was analyzed via variable temperature (VT) NMR spectroscopy, single-crystal X-ray diffraction, UV-visible spectroscopy, and DFT calculations. While small and strongly nucleophilic phosphines, such as PMe3, led to the formation of a Lewis acid-base adduct, frustrated Lewis pairs (FLPs) were observed for sterically hindered bases such as P( t Bu)3. The TOTA+-P( t Bu)3 FLP was characterized as an encounter complex, and found to promote the heterolytic cleavage of disulfide bonds, formaldehyde fixation, dehydrogenation of 1,4-cyclohexadiene, heterolytic cleavage of the C-Br bonds, and interception of Staudinger reaction intermediates. Moreover, TOTA+ and NHC were found to first undergo single-electron transfer (SET) to form [TOTA]·[NHC]˙+, which was confirmed via electron paramagnetic resonance (EPR) spectroscopy, and subsequently form a [TOTA-NHC]+ adduct or a mixture of products depending the reaction conditions used.

Redox activity of a dissymmetric ligand bridging divalent ytter-bium and reactive nickel fragments.

The reaction of a reactive nickel dimethyl 1 bearing a redox-active, dissymmetric ligand, which is obtained by deprotonation of 2-pyrimidin-2-yl-1H-benzimidazole (Hbimpm) with a divalent lanthanide complex, Cp*2Yb(OEt2), affords an unprecedented, trimeric 2 with C(sp3)-C(sp3) bond formation between two ligands in an exo position. Meanwhile, the transient, dimeric species 3 can be isolated with the same ligand coupling fashion, however, with a drastic distorsion angle of the bimpm ligand and reactive NiMe2 fragment, revealing the possible mechanism of this rearrangement. A much more stable dimeric congener, 5, with an exo ligand coupling, is synthesized in the presence of 18-crown-6, which captures the potassium counter ion. The C-C coupling formation between two bimpm ligands results from the effective electron transfer from divalent lanthanide fragments. Without the divalent lanthanide, the reductive coupling occurs on a different carbon of the ligand, nicely showing the modulation of the spin density induced by the presence of the lanthanide ion. The electronic structures of these complexes are investigated by magnetic study (SQUID), indicating a 2F7/2 ground state for each ytterbium in all the heterometallics. This work firstly reports ligand coupling reactivity in a redox-active, yet dissymmetric system with divalent organolanthanides, and the reactive nickel moiety can impact the intriguing transition towards a stable homoleptic, trinulear lanthanide species.

Bis-cyclooctatetraenyl Thulium(II): Highly Reducing Lanthanide Sandwich Single Molecule Magnets.

Divalent lanthanide organometallics are well-known highly reducing compounds usually used for single electron transfer reactivity and small molecule activation. Thus, their very reactive nature prevented for many years the study of their physical properties, such as magnetic studies on a reliable basis. In this article, the access to rare organometallic sandwich compounds of TmII with the cyclooctatetraenyl (Cot) ligand impacts on the use of divalent organolanthanide compounds as an additional strategy for the design of performing Single Molecule Magnets (SMM). Herein, the first divalent thulium sandwich complex with f13 configuration behaving as a Single Molecule Magnet in absence of DC field is highlighted.

Influence of a Lanthanide Ion on the Ni Site of a Heterobimetallic 3d-4f Mabiq Complex.

This work presents the synthesis and characterization of a 3d-4f bimetallic complex based on the redox-active macrocyclic biquinazoline ligand, Mabiq. The mixed Yb-Ni complex, [(Cp*)2Yb(Mabiq)Ni]BArF (3), was synthesized upon reaction of [NiII(Mabiq)]BArF (2) with (Cp*)2YbII(OEt2). The molecular structures of 3 and its sister complex, [(Cp*)2Yb(Mabiq)Ni][(Cp*)2Yb(OTf)2] (1), confirmed the presence of a Yb(III) center and a reduced Ni-Mabiq unit. Spectroscopy (absorption and NMR), cyclic voltammetry, and magnetic susceptibility studies were employed to analyze the electronic structure of 3, which is best described by the [(Cp*)2YbIII(Mabiq•)NiII]+ formulation. Notably, the ligand-centered radical is delocalized over both the diketiminate and bipyrimidine units of the Mabiq ligand. The magnetic susceptibility and variable temperature NMR studies for 3 denote coupling between the Ni-Mabiq site and the peripheral Yb center-previously unobserved in 3d-3d Mabiq complexes. The complex nature of the exchange interactions is highlighted by the multiconfigurational ground state for 3, comprising nearly degenerate singlet and triplet states.

FeIII and FeII Phosphasalen Complexes: Synthesis, Characterization, and Catalytic Application for 2-Naphthol Oxidative Coupling.

We report on the synthesis and characterization of three iron(III) phosphasalen complexes, [FeIII (Psalen)(X)] differing in the nature of the counter-anion/exogenous ligand (X- =Cl- , NO3 - , OTf- ), as well as the neutral iron(II) analogue, [FeII (Psalen)]. Phosphasalen (Psalen) differs from salen by the presence of iminophosphorane (P=N) functions in place of the imines. All the complexes were characterized by single-crystal X-ray diffraction, UV/Vis, EPR, and cyclic voltammetry. The [FeII (Psalen)] complex was shown to remain tetracoordinated even in coordinating solvent but surprisingly exhibits a magnetic moment in line with a FeII high-spin ground state. For the FeIII complexes, the higher lability of triflate anion compared to nitrate was demonstrated. As they exhibit lower reduction potentials compared to their salen analogues, these complexes were tested for the coupling of 2-naphthol using O2 from air as oxidant. In order to shed light on this reaction, the interaction between 2-naphthol and the FeIII (Psalen) complexes was studied by cyclic voltammetry as well as UV/Vis spectroscopy.

Persistent, highly localized, and tunable [4]helicene radicals.

Persistent organic radicals have gained considerable attention in the fields of catalysis and materials science. In particular, helical molecules are of great interest for the development and application of novel organic radicals in optoelectronic and spintronic materials. Here we report the syntheses of easily tunable and stable neutral quinolinoacridine radicals under anaerobic conditions by chemical reduction of their quinolinoacridinium cation analogs. The structures of these [4]helicene radicals were determined by X-ray crystallography. Density functional theory (DFT) calculations, supported by electron paramagnetic resonance (EPR) measurements, indicate that over 40% of spin density is located at the central carbon of our [4]helicene radicals regardless of their structural modifications. The localization of the charge promotes a reversible oxidation to the cation upon exposure to air. This unusual reactivity toward molecular oxygen was monitored via UV-Vis spectroscopy.

Reactive Heterobimetallic Complex Combining Divalent Ytterbium and Dimethyl Nickel Fragments.

This article presented the synthesis and characterization of original heterobimetallic species combining a divalent lanthanide fragment and a divalent nickel center bridged by the bipyrimidine ligand, a redox-active ligand. X-ray crystal structures were obtained for the Ni monomer (bipym)NiMe2, 1, as well as the heterobimetallic dimer compounds, Cp*2Yb(bipym)NiMe2, 2, along with 1H solution NMR, solid-state magnetic data, and DFT calculations only for 1. The reactivity with CO was investigated on both compounds and the stoichiometric acetone formation is discussed based on kinetic and mechanistic studies. The key role of the lanthanide fragment was demonstrated by the relatively slow CO migratory insertion step, which indicated the stability of the intermediate.

Reversible electron transfer in organolanthanide chemistry.

This article relates the synthesis and characterization of novel heterobimetallic complexes containing a low-valent lanthanide, a tetradentate redox non-innocent ligand, viz. the 4,5,9,10-tetraazaphenanthrene, taphen ligand and transition metal fragments of PdMe2 and PtMe2. The experimental results are supported by a theoretical study. Investigation of their reduction properties allowed the formation of isostructural original heterotrimetallic complexes containing two Cp*2Yb fragments and the (taphen)MMe2 (M = Pd and Pt) motifs. These complexes are stable in non-coordinating solvent such as toluene but decompose in coordinating solvents such as thf. Investigation of the internal electron transfer shows that the taphen ligand behaves as a two-electrons reservoir but is capable of transferring back only one electron in thf. This reversible electron(s) transfer is rare in organolanthanide chemistry and show the potential interest of these complexes in reductive chemistry. Additionally, the trinuclear complexes feature odd X-ray crystal structures in which a deviation of symmetry is observed. The latter observation was studied in depth using quantum chemistry calculations highlighting the role of non-covalent weak interactions.

Electronic Structure and Reactivity of One-Electron-Oxidized Copper(II) Bis(phenolate)-Dipyrrin Complexes.

The sterically hindered bis(phenol)-dipyrrin ligands HLH3 and PhLH3 were reacted with 1 equiv of copper(II) under ambient conditions to produce the copper radical complexes [Cu(HL)] and [Cu(PhL)]. Their X-ray crystal structures show relatively short C-O bond distances (mean bond distances of 1.287 and 1.291 Å), reminiscent of mixed pyrrolyl-phenoxyl radical species. Complexes [Cu(HL)] and [Cu(PhL)] exhibit rich electronic spectra, with an intense near-IR (NIR) band (ε > 6 mM-1 cm-1) at 1346 and 1321 nm, respectively, assigned to a ligand-to-ligand charger-transfer transition. Both show a reversible oxidation wave ( E1/21,ox = 0.05 and 0.04 V), as well as a reversible reduction wave ( E1/21,red = -0.40 and -0.56 V versus ferrocenium/ferrocene, respectively). The cations ([Cu(HL)]+ and [Cu(PhL)]+) and anions ([Cu(HL)]- and [Cu(PhL)]-) were generated. They all display an axial ( S = 1/2) signal with a copper hyperfine structure in their electron paramagnetic resonance spectra, consistent with ligand-centered redox processes in both reduction and oxidation. Complex [Cu(HL)](SbF6) was cocrystallized with [Cu(HL)]. Oxidation is accompanied by a slight contraction of both the C-O bonds (mean bond distance of 1.280 Å) and the C-C bonds connecting the peripheral rings to the dipyrrin. The cations show vis-NIR bands of up to 1090 nm due to their quinoidal nature. The anions do not show a significant band above 700 nm, in agreement with their bis(phenolate)-dipyrrin character. The radical complexes efficiently catalyze the aerobic oxidation of benzyl alcohol, 1-phenylethanol, and unactivated 2-phenylethanol in basic conditions.

Ni(II) Complexes of the Redox-Active Bis(2-aminophenyl)dipyrrin: Structural, Spectroscopic, and Theoretical Characterization of Three Members of an Electron Transfer Series.

The sterically hindered bis(2-aminophenyl)dipyrrin ligand H3NL was prepared. X-ray diffraction discloses a bifurcated hydrogen bonding network involving the dipyrrin and one aniline ring. The reaction of H3NL with one equivalent of nickel(II) in the air produces a paramagnetic neutral complex, which absorbs intensively in the Vis-NIR region. Its electron paramagnetic resonance spectrum displays resonances at g1 = 2.033, g2 = 2.008, and g3 = 1.962 that are reminiscent of an (S = 1/2) system having a predominant organic radical character. Both the structural investigation (X-ray diffraction) and density functional theory calculations on [NiII(NL•)] points to an unprecedented mixed "pyrrolyl-anilinyl" radical character. The neutral complex [NiII(NL•)] exhibits both a reversible oxidation wave at -0.28 V vs Fc+/Fc and a reversible reduction wave at -0.91 V. The anion was found to be highly air-sensitive, but could be prepared by reduction with cobaltocene and structurally characterized. It comprises a Ni(II) ion coordinated to a closed-shell trianionic ligand and hence can be formulated as [NiII(NL)]-. The cation was generated by reacting [NiII(NL•)] with one equivalent of silver hexafluoroantimonate. By X-ray diffraction we established that it contains an oxidized, closed-shell ligand coordinated to a nickel(II) ion. We found that a reliable hallmark for both the oxidation state of the ligand and the extent of delocalization within the series is the bond connecting the dipyrrin and the aniline, which ranges between 1.391 Š(cation) and 1.449 Š(anion). The cation and anion exhibit a rich Vis-NIR spectrum, despite their nonradical nature. The low energy bands correspond to ligand-based electronic excitations. Hence, the HOMO-LUMO gap is small, and the redox processes in the electron transfer series are exclusively ligand-centered.

Mn(iv) and Mn(v)-radical species supported by the redox non-innocent bis(2-amino-3,5-di-tert-butylphenyl)amine pincer ligand.

The electron-rich pincer ligand 1 has been synthesized and chelated to manganese. The octahedral Mn(iv) bis(diiminosemiquinonate) and Mn(v) (diiminobenzoquinone) (diiminosemiquinonate) radicals were structurally characterized.

The structure of a one-electron oxidized Mn(iii)-bis(phenolate)dipyrrin radical complex and oxidation catalysis control via ligand-centered redox activity.

The tetradentate ligand dppH3, which features a half-porphyrin and two electron-rich phenol moieties, was prepared and chelated to manganese. The mononuclear Mn(iii)-dipyrrophenolate complex 1 was structurally characterized. The metal ion lies in a square pyramidal environment, the apical position being occupied by a methanol molecule. Complex 1 displays two reversible oxidation waves at 0.00 V and 0.47 V vs. Fc+/Fc, which are assigned to ligand-centered processes. The one-electron oxidized species 1+ SbF6- was crystallized, showing an octahedral Mn(iii) center with two water molecules coordinated at both apical positions. The bond distance analysis and DFT calculations disclose that the radical is delocalized over the whole aromatic framework. Complex 1+ SbF6- exhibits an Stot = 3/2 spin state due to the antiferromagnetic coupling between Mn(iii) and the ligand radical. The zero field splitting parameters are D = 1.6 cm-1, E/D = 0.18(1), g⊥ = 1.99 and g∥ = 1.98. The dication 12+ is an integer spin system, which is assigned to a doubly oxidized ligand coordinated to a Mn(iii) metal center. Both 1 and 1+ SbF6- catalyze styrene oxidation in the presence of PhIO, but the nature of the main reaction product is different. Styrene oxide is the main reaction product when using 1, but phenylacetaldehyde is formed predominantly when using 1+ SbF6-. We examined the ability of complex 1+ SbF6- to catalyze the isomerization of styrene oxide and found that it is an efficient catalyst for the anti-Markovnikov opening of styrene oxide. The formation of phenylacetaldehyde from styrene therefore proceeds in a tandem E-I (epoxidation-isomerization) mechanism in the case of 1+ SbF6-. This is the first evidence of control of the reactivity for styrene oxidation by changing the oxidation state of a catalyst based on a redox-active ligand.