RESUMEN

Herein we report the reduction of R-EX2 (E=P, Sb) with two equivalents of KC8 in the presence of silylene (LSiR; L=PhC(NtBu)2 ) to give Trip-P=SiL(C6 H4 PPh2 ) (1), Ter Ph-P=(tBu)SiL (2) and Ter Ph-Sb=(tBu)SiL (3). The last (3) belongs to a new class of heavier analogues of Schiff bases (>C=N-), containing a formal >Si=Sb- double bond. The theoretical calculations suggest that lone pairs on the dicoordinated group-15 centers are stabilized by hyperconjugative interactions resulting in pseudo-Si-P/Si-Sb multiple bonds which are highly reactive as indicated by the high first and second proton affinities.

RESUMEN

A successful selective reduction of X2B-Tip (Tip = 1,3,5-iPr3-C6H2, X = I, Br) with KC8 and Mg metal, respectively, in the presence of a hybrid ligand (C6H4(PPh2)LSi) leads to a stable low-valent five-membered ring as a boryl radical [C6H4(PPh2)LSiBTip][Br] (1) and neutral borylene [C6H4(PPh2)LSiBTip] (2). Compound 2 reacts with 1,4-cyclohexadiene, resulting in hydrogen abstraction to afford the radical [C6H4(PPh2)LSiB(H)Tip] (3). Quantum chemical studies reveal that compound 1 is a B-centered radical, and compound 2 is a phosphane and silylene stabilized neutral borylene in a trigonal planar environment, whereas compound 3 is an amidinate-centered radical. Although compounds 1 and 2 are stabilized by hyperconjugation and π-conjugation, they display high H-abstraction energy and basicity, respectively.

RESUMEN

We present an approach for preparing chain-type unsaturated molecules with low oxidation state Si(I) and Sb(I) supported by amidinato ligands that exploit to generate heavy analogues of ethane 1,2-diimine. The reduction of antimony dihalide (R-SbCl2) with KC8 in the presence of silylene chloride afforded L─(Cl)Si═Sb─Tip (1) and L(Cl)Si═Sb─TerPh (2), respectively. Compounds 1 and 2 further undergo reduction with KC8 to produce Tip─Sb═LSi─LSi═Sb─Tip (3) and TerPh─Sb═LSi─LSi═Sb─TerPh (4). The solid-state structures and DFT studies show that all compounds have σ-type lone pairs at each Sb atom. It forms a strong pseudo-π-bond with Si. The pseudo-π-bond is formed by the hyperconjugative donation of the π-type lone pair at Sb to the Si-N σ* MO. The quantum mechanical studies indicate that compounds 3 and 4 has delocalized pseudo-π-MOs arising from hyperconjugative interactions. Hence, 1 and 2 can be considered as isoelectronic to imine, while 3 and 4 are isoelectronic to ethane-1,2-diimine. The proton affinity studies indicate that the pseudo-π-bond resulting from the hyperconjugative interaction is more reactive than the σ-type lone pair.

RESUMEN

Herein, we report the stabilization of lithium-ion as the source of lithium to use as a trans-metalation reagent [{PhC(Nt Bu)2 Si(t Bu)Li}2 I(t BuN)2 CPh] (1). The reaction of 3 equivalents of the LSit Bu (L=PhC(Nt Bu)2 ) and lithium iodide at low temperature leads to a silylene stabilized lithium-ion with an additional coordination of amidinate ligand. Compound 1 shows two four membered and one six membered ring as confirmed by QTAIM calculations. Whereas the reaction of the LSiCl with 1.5 equivalents of carbodiimide (CyN)2 C at room temperature affords compound [PhC(Nt Bu)2 Si(Cl)(NCy)2 NCy] (2) with the CN2 SiN2 C skeleton containing silicon as a central atom. Both the compounds were fully characterized by NMR, mass spectrometry, X-ray crystallographic analysis, and quantum mechanical calculations.

RESUMEN

This work presents the different coordination nature of the bidentate ligand towards gold and silver complexes. The reaction of 1 with AuClSMe2 in dichloromethane resulted in two gold atoms containing six-membered ring PhC(NtBu)2Si-Au⋯Au-PPh2C6H4 (2). Compound 2 exhibits intramolecular aurophilic interaction (2.9987(7) Å), which is further supported by quantum chemical calculations. Moreover, the reduction of aluminium adduct 3 with AgSbF6 affords insertion of silver cation [{PhC(NtBu)2SiF2}-C6H4(PPh2)-Ag-(PPh2)C6H4{PhC(NtBu)2SiF2}]AlCl4- (4) between two phosphane. In compound 4 only two P(III) of two molecules of 1 coordinates to Ag(I), while two Si(II) remains uncoordinated and gives oxidative addition of Fluorine.

RESUMEN

Herein we report stable silicon-boron radicals of composition LSi(NMe2)-B(Br)Tip (1), LSi(NMe2)-B(I)Tip (2) LSi(tBu)-B(I)Tip (3) [L = PhC(NtBu)2]. They were prepared in high yield using a one pot reaction of LSiR, X2BTip and KC8 in a 1 : 1 : 1 molar ratio (R = tBu, NMe2; X = Br, I). The reaction of the silicon-boron radical with Br2 and Se affords the dihalogenated compound LSi(tBu)-B(Br2)Tip (4) and oxidative addition product LSi(tBu)Se (5). All the compounds were characterized by single-crystal X-ray structural analysis, electron paramagnetic resonance (EPR) analysis, elemental analysis, multinuclear NMR spectroscopy, and mass spectrometry. Quantum chemical calculations show that the B-centered radicals 1-3 are stabilised by hyperconjugative interactions.

RESUMEN

From the sodium sodate precursor [(Na(thf)6][Na{(4-Me-NCOC6H3)2CH}2] (1) three isostructural dinuclear lanthanide complexes [(µ-Cl)LnIII{(4-MeNCOC6H3)2CH}2]2 with Ln = Gd (2), Dy (3), and Er (4) based on the N,N'-chelating monoanionic bis(4-methylbenzoxazol-2-yl)methanide ligand (titled "Mebox") were synthesized and characterized by X-ray diffraction and magnetic measurements. The sodium precursor 1 was analyzed via X-ray diffraction and diffusion-ordered NMR spectroscopy experiments (DOSY-NMR) in order to investigate its aggregation in solution and the solid state. The sodium analog [(thf)3Na(NCOC6H4)2CH] (1') based on the bis(benzoxazol-2-yl)-methanide ligand (titled "box") was prepared and analyzed for comparison reasons. From the lanthanide derivatives 2-4, the DyIII complex 3 displays slow relaxation of magnetization at zero field, with a relaxation barrier of U = 315.7 cm-1. The coupling strength between the two lanthanide centers was estimated with the GdIII equivalent 2, giving a weak antiferromagnetic coupling of J = -0.035 cm-1.

RESUMEN

Based on the potassium [{S(tBuN)2 (tBuNH)}2 K3 (tmeda)-K3 {(HNtBu)(NtBu)2 S}2 ] (1) and sodium precursors [S(tBuN)3 (thf)3 -Na3 SNa3 (thf)3 (NtBu)3 S] (2), [S(tBuN)3 (thf)3 Na3 {(HNtBu)(NtBu)2 S}] (3) and [(tmeda)3 S-{Na3 (NtBu)3 S}2 ] (4) the syntheses and magnetic properties of three mixed metal triimidosulfite based alkali-lanthanide-metal-cages [(tBuNH)Dy{K(0.5tmeda)}2 {(NtBu)3 S}2 ]n (5) and [ClLn{Na(thf)}2 {(NtBu)3 S}2 ] with Ln=Dy (6), Er (7) are reported. The corresponding potassium (1) and sodium (2-4) based cages are characterized through XRD and NMR experiments. Preventing lithium chloride co-complexation led to a significant increase of SMM performance to previously reported sulfur-nitrogen ligands. The subsequent DyIII -complexes 5 and 6 display slow relaxation of magnetization at zero field, with relaxation barriers U=77.0 cm-1 for 5, 512.9 and 316.3 cm-1 for 6, respectively. Significantly, the latter complex 6 also exhibits a butterfly-shaped hysteresis up to 7 K.

RESUMEN

The reaction of potassium metal with sulfurtriimide S(Nt Bu)3 (II) gives the long elusive deep blue cage radical [K3 {(Nt Bu)3 S}2 ]. (1_K) that crystallizes at -35 °C from toluene solution. The subsequent physical characterization via X-ray structure analysis, UV/Vis-, and EPR spectroscopy from solution reveals the existence of one unpaired electron delocalized within the whole cage, i.e. coupling with the six nitrogen atoms, as well as the three potassium atoms caped by the two SN3 ligands. The present X-ray structure analysis further supports previous assumptions made on the parent compound 1_Li obtained from [Li4 {(Nt Bu)3 S}2 ] (I) and finally elucidates the structural arrangement of the SN3 caps and alkali metals in such radical cage species.

RESUMEN

Two series a and b of 3d metal based complexes 1-4 [MII{(4-R-NCOC6H4)2CH}2], (with M = Mn (1), Fe (2), Co (3), Ni (4) and R = H (a) or Me (b)) were synthesised and structurally characterized. The complexes were found to crystallize differently depending on the dication ionic radius and the ligand substitution. All complexes showed remarkable X-ray diffraction resolution that will allow further advanced diffraction experiments. Subsequently, their spectroscopic and magnetic properties were analysed. Complexes 3a and 3b notably show slow magnetic relaxation of their magnetization and represent simple model systems relaxing through a phonon-bottleneck process (3a) or as a field-induced single-molecule magnet (3b, Ueff = 45.0 cm-1). Remarkably, the magnetic anisotropy in the manganese complex 1b results in induced slow magnetic relaxation. The influence of the dual 4-methylation of the ligands was investigated and found to generate important variations in the physical features of the corresponding complexes. Accessible via one-pot synthesis, these are highly robust against oxidation and moisture. Through smart ligand engineering, they represent stable and tuneable compounds for benchmarking purposes through standard and less-standard characterization methods.

RESUMEN

Single-molecule magnets (SMMs) harbour vast opportunities for potential pioneering applications upon optimization like big data storage and quantum computing. Lanthanides were found to be highly suitable candidates in the design of such molecules, as they intrinsically hold a large unquenched orbital momentum and a strong spin-orbit coupling, warranting a high magnetic anisotropy. An indispensable element in successfully tailoring SMMs is the ligand design. Polyimido sulfur ligands offer a promising choice because the polar S+-N--bond facilitates both electronic and geometric adaptability to various f-metals. In particular, the acute N-Ln-N bite angle generates advantageous magnetic properties. The [Ph2PCH2S(NtBu)3]- anion, introduced from [(thf)3K{Ph2PCH2S(NtBu)3}] (2) to a series of complexes [ClLn{Ph2PCH2S(NtBu)3}2] with Ln = Tb (3a), Dy (3b), Er (3c), Ho (3d), and Lu (3e), provides tripodal shielding of the metal's hemisphere as well as a side-arm donation of a soft phosphorus atom. For the Tb and Er complexes 3a and 3d, slow magnetic relaxation (Ueff = 235 and 34.5 cm-1, respectively) was only observed under an applied dc field. The dysprosium congener 3b, however, is a true SMM with relaxation at zero field (Ueff = 66 cm-1) and showing a butterfly hysteresis close to 3.5 K. Upon magnetic dilution with the diamagnetic and isostructural lutetium complex 3e or application of a magnetic field, the energy barrier to spin reversal is increased to 74 cm-1.

RESUMEN

Herein, we report the stabilization of nitrene reagents as the source of a nitrogen atom to synthesize nitrogen-incorporated R1 LSi-N←SiLR2 (1) [L=PhC(NtBu)2 ; R1 =NTMS2 , R2 =NTMS]. Compound 1 is synthesized by reacting LSi(I)-SiI L with 3.1 equivalents of Me3 SiN3 at low temperature to afford a triene-like structural framework. Whereas the reaction of the LSi(I)-SiI L with 2.1 equivalents of Me3 SiN3 at room temperature produced silaimine 2 with a central four-membered Si2 N2 ring which is accompanied by a silylene LSi and a cleaved silylene fragment. 1 further reacts with AgOTf at room temperature to yield compound 3 which shows coordination of nitrene to silver with the triflate salt. The compounds 1 and 2 were fully characterized by NMR, mass spectrometry, and X-ray crystallographic analysis. The quantum mechanical calculations reveal that compounds 1 and 2 have dicoordinated monovalent N atoms having two active lone pairs of electrons. These lone pairs are stabilized by hyperconjugative interactions.

RESUMEN

The synthesis and magnetic characterization of three novel Dy compounds, [Dy{PPh2S(NtBu)2}2(µ-Cl2)Li(THF)2] (1), [Dy{PhS(NtBu)2}2(µ-Cl2)Li(THF)2] (2), and [Dy{MeS(NtBu)3}2(µ-Cl2)Li(THF)2] (3), based on the sulfur-nitrogen ligands RS(NtBu)x- (where R = PPh2, x = 2 for (1); R = Ph, x = 2 for (2); and R = Me, x = 3 for (3)) are reported. They represent rare examples of lanthanide-based complexes containing sulfur-nitrogen ligands, whose suitability to enhance the magnetic anisotropy in 3d metals was only recently established. Changes in the ligand field environment drastically affect the magnetic properties, with compounds 1 and 2 displaying field-induced single-molecule magnet (SMM) behavior, while compound 3 shows slow relaxation at zero field. These trends strongly suggest that ligand engineering strategies toward linear dysprosium complexes, similar to those for dysprosocenium complexes, should enhance the SMM performances of SN-based lanthanide compounds.

RESUMEN

Herein, we report on a facile and selective one-pot synthetic route to silicon-boron radicals. Reduction of Br2BTip (Tip = 2,4,6-iPrC6H2) with KC8 in the presence of LSi-R affords LSi(tBu)-B(Br)Tip (1) and LSi(N(TMS)2)-B(Br)Tip (2) [L = PhC(NtBu)2]. These first examples of silicon-boron isolated radical species feature spin density on the silicon and boron atoms. 1 and 2 exhibit extraordinary stability to high temperatures under inert conditions in solution and air stability in the solid state. Both radicals have been isolated and fully characterized by electron paramagnetic resonance spectroscopy, SQUID magnetometry, mass spectrometry, cyclic voltammetry, single-crystal X-ray structure analysis, and density functional theory calculations. Moreover, compound 1 exhibits one-electron transfer when treated with 1 equiv of AgSO3CF3 and [Ph3C]+[B(C6F5)4]-, respectively, resulting in the corresponding cations [LSi(tBu)-B(Br)Tip]+[CF3SO3]- (3) and [LSi(tBu)-B(Br)Tip]+[B(C6F5)4]- (4). Compounds 3 and 4 have been characterized with multinuclear NMR and mass spectrometry.

RESUMEN

We prepared four new complexes, 4a,b and 5a,b, from polyimido sulfur-centered ligands with FeII and CoII amides. Their molecular structures were elucidated by single-crystal X-ray diffraction. Cobalt magnetic investigations and multiconfigurational calculations provided insight into magneto-structural correlations between the acute N,N' chelating bite angle and P-side arm donation. The deviation from an ideal trigonal planar geometry and the magnetic performance correlated in an unprecedented manor. Mononuclear cobalt species 4b and 5b showed slow magnetic relaxation under a small applied dc field with energy barriers of up to 33.0 and 21.9 cm-1, respectively. Although they possess some of the largest zero-field splitting parameters among three-coordinate cobalt single-ion magnets, both theory and experiment suggest that the high rhombicity (E/D) hampers large effective energy barriers to spin reversal at zero field from being obtained.

RESUMEN

This work describes the synthesis and coordination behavior of a new mixed-donor ligand PhC(NtBu)2 SiC6 H4 PPh2 (1) containing both silylene and phosphine donor sites. Ligand 1 was synthesized from a reaction of ortho-lithiated diphenylphosphinobenzene (LiC6 H4 PPh2 ) with chlorosilylene (PhC(NtBu)2 SiCl). Treatment of 1 with Se and GeCl2 resulted in SiIV compounds 2 and 3 by selective oxidation of the silylene donor. This strong σ-donor ligand induces dissociation of CuCl and PhBCl2 leading to formation of ionic complexes 4 and 5 respectively. The reaction of 1 with ZnCl2 and AlCl3 resulted in the formation of chelate complexes 5 and 7, respectively, while treatment with EtAlCl2 and GaCl3 forms monodentate complexes 8 and 9. X-ray analysis of 4 showed that the copper is in the spiro center of the two five-membered rings. Moreover, the copper(I)chloride has not been oxidized but dissociates to Cu+ and [CuCl2 ]- . All the compounds are well characterized by mass spectrometry, elemental analysis, NMR spectroscopy, and single-crystal X-ray diffraction studies.

RESUMEN

The (hetero)bimetallic complexes [Cl2Mn(NtBu)2S(tBuN)2Mn{ClLi(THF)3}2] (1), [(acac)Co(NtBu)2S(tBuN)2Co(acac)] (2), and [(acac)Co(NtBu)2S(tBuN)2Li(THF)2] (3), with THF = tetrahydrofuran and acac = acetylacetonate [H2C(C(O)Me)2], were synthesized and investigated for their magnetic properties. While the two different MnII sites in 1 gave a weak coupling of J = -1.00 cm-1, we could observe an appreciable antiferromagnetic coupling of J = -6.08 cm-1 between the two CoII cations in 2, proving the tetraimido sulfate anion to be a challenging but promising linker to enhance magnetic communication between paramagnetic centers. The heterobimetallic complex 3 seems a versatile platform for magnetically interesting d/d, f/d, or f/f mixed-metal complexes.

RESUMEN

Calcium coordination solids were synthesized and evaluated for delivery of olsalazine (H4 olz), an anti-inflammatory compound used for treatment of ulcerative colitis. The materials include one-dimensional Ca(H2 olz)⋅4 H2 O chains, two-dimensional Ca(H2 olz)⋅2 H2 O sheets, and a three-dimensional metal-organic framework Ca(H2 olz)⋅2DMF (DMF=N,N-dimethylformamide). The framework undergoes structural changes in response to solvent, forming a dense Ca(H2 olz) phase when exposed to aqueous HCl. The compounds Ca(H2 olz)⋅x H2 O (x=0, 2, 4) were each pressed into pellets and exposed to simulated gastrointestinal fluids to mimic the passage of a pill from the acidic stomach to the pH-neutral intestines. All three calcium materials exhibited a delayed release of olsalazine relative to Na2 (H2 olz), the commercial formulation, illustrating how formulation of a drug within an extended coordination solid can serve to tune its solubility and performance.

Asunto(s)

Ácidos Aminosalicílicos/química , Calcio/química , Complejos de Coordinación/química , Preparaciones de Acción Retardada , Portadores de Fármacos/química , Concentración de Iones de Hidrógeno

RESUMEN

The drug olsalazine (H4olz) was employed as a ligand to synthesize a new series of mesoporous metal-organic frameworks that are expanded analogues of the well-known M2(dobdc) materials (dobdc(4-) = 2,5-dioxido-1,4-benzenedicarboxylate; M-MOF-74). The M2(olz) frameworks (M = Mg, Fe, Co, Ni, and Zn) exhibit high surface areas with large hexagonal pore apertures that are approximately 27 Å in diameter. Variable temperature H2 adsorption isotherms revealed strong adsorption at the open metal sites, and in situ infrared spectroscopy experiments on Mg2(olz) and Ni2(olz) were used to determine site-specific H2 binding enthalpies. In addition to its capabilities for gas sorption, the highly biocompatible Mg2(olz) framework was also evaluated as a platform for the delivery of olsalazine and other encapsulated therapeutics. The Mg2(olz) material (86 wt % olsalazine) was shown to release the therapeutic linker through dissolution of the framework under simulated physiological conditions. Furthermore, Mg2(olz) was used to encapsulate phenethylamine (PEA), a model drug for a broad class of bioactive compounds. Under simulated physiological conditions, Mg2(olz)(PEA)2 disassembled to release PEA from the pores and olsalazine from the framework itself, demonstrating that multiple therapeutic components can be delivered together at different rates. The low toxicity, high surface areas, and coordinatively unsaturated metal sites make these M2(olz) materials promising for a range of potential applications, including drug delivery in the treatment of gastrointestinal diseases.

Asunto(s)

Ácidos Aminosalicílicos/química , Materiales Biocompatibles/química , Sistemas de Liberación de Medicamentos , Adsorción , Sitios de Unión , Química Orgánica , Portadores de Fármacos , Enfermedades Gastrointestinales/tratamiento farmacológico , Humanos , Hidrógeno/química , Ligandos , Estructuras Metalorgánicas , Metales/química , Compuestos Orgánicos/química , Fenetilaminas/química , Ácidos Ftálicos , Espectrofotometría Infrarroja , Propiedades de Superficie