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1.
J Shoulder Elbow Surg ; 32(1): 159-167, 2023 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-36167289

RESUMEN

BACKGROUND: The role of the lateral part of the distal triceps as a stabilizer in the lateral collateral ligament-deficient elbow and whether its effect in improving the stability is independent of that of the anconeus are unclear. METHODS: Seven cadaveric elbows were tested under gravity varus stress using a custom-made machine designed to simulate muscle loads while allowing passive flexion of the elbow. An injury model was created by sectioning the lateral collateral ligament and sparing the common extensor origin. The lateral part of the distal triceps tendon was loaded sequentially with 0 N, 10 N, 25 N, and 40 N. Each stage of the lateral part of the distal triceps loading was tested with the anconeus unloaded (inactive) or with a 25-N load applied (active). Articular contact pressures on the coronoid, the medial facet, and the lateral facet were collected and processed using Tekscan sensors and software. RESULTS: A significant decrease in the mean coronoid contact pressure was seen with sequential loading of the lateral part of the distal triceps (P < .001). The ratio of medial to lateral facet contact pressures significantly decreased with sequential loading of the lateral part of the distal triceps (P < .001), indicating a better distribution of the contact pressure between the medial and lateral facets as the lateral part of the distal triceps was loaded. These effects were statistically significant, both with and without anconeus loading. There was no significant modification of the effect of the lateral part of the distal triceps loading on the contact pressure by the anconeus loading (P = .47). However, with active anconeus loading, the contact pressure and the ratio of medial to lateral facet contact pressures were significantly lower for any stage of lateral triceps loading (P < .001), indicating a synergistic effect of the anconeus. CONCLUSIONS: In a lateral collateral ligament-deficient elbow, the lateral part of the distal triceps loading prevents the increased contact pressure on the coronoid under varus stress and improves the distribution of contact pressures on the coronoid. Anconeus loading further decreases and improves the distribution of the contact pressures; however, its effect is independent of that of the lateral part of the distal triceps. These results substantiate a role of the lateral part of the distal triceps as a dynamic constraint against elbow varus and have clinical implications for prevention and rehabilitation of elbow instability.


Asunto(s)
Articulación del Codo , Inestabilidad de la Articulación , Humanos , Tendones , Gravitación , Programas Informáticos
2.
Org Biomol Chem ; 20(21): 4289-4292, 2022 06 01.
Artículo en Inglés | MEDLINE | ID: mdl-35574705

RESUMEN

A series of C-functionalized ß-ketoimine compounds at the terminal methyl groups of the ß-ketoimine precursor LphH2 (Lph = C6H4[NC(Me)CHC(Me)O]2) were prepared. This convenient transformation was realized via straightforward double alkylation on the terminal Cα of a novel bis-dianionic ß-ketoiminate lithium complex [Lph'Li4(THF)4]2 (Lph' = C6H4[NC(Me)CHC(O)CH2]2) followed by hydrolysis.


Asunto(s)
Alquilación
3.
Org Biomol Chem ; 19(34): 7432-7437, 2021 09 14.
Artículo en Inglés | MEDLINE | ID: mdl-34397075

RESUMEN

A highly efficient cyanosilylation protocol mediated by the easily available n-BuLi with a wide range of aldehydes and ketones was developed. This protocol features excellent yields with very low n-BuLi loadings (0.01-0.05 mol%) at room temperature, solvent-free process, good chemo-/regio-selectivity and functional group tolerance and scalability. A possible reaction pathway based upon stoichiometric reactivity was put forward.

4.
J Org Chem ; 85(16): 10504-10513, 2020 Aug 21.
Artículo en Inglés | MEDLINE | ID: mdl-32589850

RESUMEN

Four chiral dinuclear rare-earth metal complexes [REL1]2 (RE = Y(1), Eu(2), Nd(3), La (4)) stabilized by Trost proligand H3L1 (H3L1 = (S,S)-2,6-bis[2-(hydroxydiphenylmethyl)pyrrolidin-1-ylmethyl]-4-methylphenol) were first prepared, and all were characterized by X-ray diffraction. Complex 4 was employed as the catalyst for enantioselective hydroboration reaction of substituted ketones, and the corresponding secondary alcohols with excellent yields and high ee values were obtained using reductant HBpin. The same result was also achieved using the combination of lanthanium amides La[N(SiMe3)2]3 with Trost proligand H3L1 in a 1:1 molar ratio. The experimental findings and DFT calculation revealed the possible mechanism of the enantioselective hydroboration reaction and defined the origin of the enantioselectivity in the current system.

5.
Acta Neurochir (Wien) ; 161(5): 899-906, 2019 05.
Artículo en Inglés | MEDLINE | ID: mdl-30877474

RESUMEN

BACKGROUND: Traumatic brachial plexus injuries are severe lesions, and the incidence of these injuries has been increasing in recent years. METHODS: The clinical data of 510 operated patients with brachial plexus injury recruited from 74 hospitals in Guangxi from 2004 to 2016 were retrospectively studied. RESULTS: Our study included 447 males and 63 females, with an average age of 29.04 years. Traffic accidents were the most common cause of injury (64.71%), especially motorcycle accidents. Closed injuries accounted for 88.24% of cases, and 83.53% of patients had associated injuries, the most common of which were fractures (76.27%). The preoperative predictive value of root injury of MRI and CT was 74.71% and 71.28%, respectively. 44.71% of patients underwent an initial operation within 6 months after the trauma. Regarding the surgery, neurolysis alone, brachial plexus reconstruction, and free functioning gracilis graft accounted for 16.67%, 75.50%, and 4.51%, respectively. A total of 415 patients were followed up with an average time of 47.95 (25-68) months, and anxiety or depression were found among 81.20% of them. Two hundred seventy-six patients suffered from nerve pain, with mild pain present in 67.03% of patients. Additionally, 347 patients were followed up for more than 3 years, 76.81% of patients with C5-C6 injury recovery to useful function, and the procedure of neurolysis alone demonstrated the best efficacy (79.45%). CONCLUSIONS: Brachial plexus injury is still a challenging trauma for surgeons, and traffic accidents are the dominant cause. Timely and effective surgery is important for functional limb recovery.


Asunto(s)
Neuropatías del Plexo Braquial/cirugía , Plexo Braquial/lesiones , Fracturas Óseas/cirugía , Procedimientos Neuroquirúrgicos/efectos adversos , Complicaciones Posoperatorias/epidemiología , Accidentes de Tránsito , Adulto , Plexo Braquial/cirugía , Neuropatías del Plexo Braquial/etiología , China , Femenino , Fracturas Óseas/complicaciones , Humanos , Masculino , Persona de Mediana Edad , Resultado del Tratamiento
6.
J Org Chem ; 83(17): 10677-10683, 2018 Sep 07.
Artículo en Inglés | MEDLINE | ID: mdl-30070486

RESUMEN

Highly efficient and selective hydroboration of aldehydes and ketones with HBpin is achieved by using the simple and convenient n-BuLi as a catalyst. The reaction proceeds rapidly with low catalyst loading (0.1-0.5 mol %) under mild conditions. Key features include the high catalytic efficiency, exceptional functional group compatibility, ample substrate scope, and high selectivity for aldehydes over ketones. Computational studies were carried out to provide a mechanistic insight into the n-BuLi catalyzed hydroboration of aldehydes/ketones with HBpin.

7.
Org Biomol Chem ; 16(15): 2787-2791, 2018 04 18.
Artículo en Inglés | MEDLINE | ID: mdl-29611860

RESUMEN

Homoleptic lanthanide complexes coordinated by a Me-substituted Cp ligand [(MeCp)3Ln] demonstrate unprecedentedly high efficiency in catalyzing the hydroboration of aldehydes and ketones with pinacolborane. This protocol is also applicable for the hydroboration of aryl-substituted imines. In addition, broad functional group compatibility and excellent chemoselectivity is also achieved. DFT calculations are employed to shed light on the reaction mechanism.

8.
Org Biomol Chem ; 15(18): 3968-3974, 2017 May 10.
Artículo en Inglés | MEDLINE | ID: mdl-28443907

RESUMEN

Lanthanide amide-catalyzed one-pot reaction of isatins, dialkyl phosphite, and activated alkenes was developed and a series of spiro[cyclopropan-1,3'-oxindoles] were obtained in moderate to excellent yields. The reaction is stereoselective and the two substituents at the 2 and 3-positions of the cyclopropane in the major product are in the trans configuration. A four-step mechanism involving the Pudovik reaction, Brook rearrangement, Michael addition, and intramolecular nucleophilic substitution is proposed, and an umpolung strategy was used in the process.

9.
Inorg Chem ; 53(1): 105-15, 2014 Jan 06.
Artículo en Inglés | MEDLINE | ID: mdl-24313811

RESUMEN

Two divalent ytterbium (Yb(II)) complexes, 1 and 2, supported by new [ONOO]-type amine bis(phenolate) ligands L(a,b) were synthesized in good yield by an amine elimination reaction of Yb(II)(N(SiMe3)2)2(TMEDA) (TMEDA = tetramethylethylenediamine) with one equivalent of the ligand precursor. X-ray structural determination showed complexes 1 and 2 both have a monomeric structure. Each adopts distorted octahedral coordination geometry around the six-coordinate Yb(II) ion. Two new trivalent ytterbium (Yb(III)) aryloxide complexes, 4 and 5, bearing [ONOO]-type amine bis(phenolate) ligands L(c) and L(d) were prepared by double-protonation reaction of Yb(C5H5)3THF with one equivalent of the ligand precursor, then one equivalent of phenol. Complex 4 has a symmetric dimeric structure with a Yb2O2 core bridging through the oxygen atoms of the OC6H4-4-CH3 groups. Complex 5 is a THF-solvated monomer. Each six-coordinated Yb(III) ion in both complexes adopts a distorted octahedron. All the complexes synthesized together with the known Yb(II) complex 3 were evaluated in the ring-opening polymerization (ROP) of rac-lactide (rac-LA). Complexes 1 and 4 were found to be extremely active for controlled ROP of rac-LA, as judged by narrow molar mass distributions (Mw/Mn: 1.07-1.16 for complex 1 and 1.07-1.10 for complex 4) and experimental molar mass Mn,exp values in good agreement with theoretic Mn,calcd values calculated on a single PLA chain produced per metal center of initiator. Complex 5 is less controlled. Complexes 1, 4, and 5 exhibited the same high stereoselectivity to give heterotactic polylactide with a Pr (probability of racemic enchainment of monomer units) ranging from 0.97 to 0.99. Dramatic decreases in activity and stereoselectivity were found for complexes 2 (Pr = 0.82) and 3 (Pr = 0.67), indicating the framework of L in the unit of [YbL] is crucial for determining activity and stereoselectivity of either Yb(II) or Yb(III) complexes.


Asunto(s)
Aminas/química , Complejos de Coordinación/química , Dioxanos/síntesis química , Fenoles/química , Iterbio/química , Catálisis , Complejos de Coordinación/síntesis química , Cristalografía por Rayos X , Dioxanos/química , Modelos Moleculares , Estructura Molecular , Polimerizacion , Estereoisomerismo
10.
Front Pediatr ; 11: 1043442, 2023.
Artículo en Inglés | MEDLINE | ID: mdl-36846165

RESUMEN

Carpal tunnel syndrome (CTS) is an upper extremity median nerve entrapment disorder that is rare in children and adolescents. Anatomical variations of the wrist, such as anomalous muscles, persistent median artery (PMA), and bifid median nerves (BMN), are rare etiology of CTS. Coexistence of all three variants combined with CTS in adolescents has been rarely reported. Case description: A 16-year-old right-hand dominant male presented to our clinic with several years of bilateral thenar muscle atrophy and weakness but no paresthesia or pain in his both hands. Ultrasonography showed that the right median nerve become significantly thinner, and the left median nerve was split into two branches by PMA. Magnetic resonance imaging (MRI) revealed that anomalous muscles in the bilateral wrist extending to the carpal tunnel, causing compression of the median nerve. Considering the possibility of CTS clinically, the patient underwent bilateral open carpal tunnel release without resection of anomalous muscles and PMA. The patient has no discomfort after 2 years. This suggests that anatomical variations of the carpal tunnel may contribute to CTS, which can be confirmed by preoperative ultrasonography and MRI, and the possibility of carpal tunnel anatomical variations should be considered when CTS occurs in adolescents. Open carpal tunnel release is an effective treatment for juvenile CTS without the need to resect abnormal muscle and PMA during the operation.

11.
Diabetes Metab Syndr Obes ; 13: 405-412, 2020.
Artículo en Inglés | MEDLINE | ID: mdl-32110073

RESUMEN

OBJECTIVE: To analyse the clinical features of pneumomediastinum associated with DKA (diabetic ketoacidosis) to improve clinicians' understanding of the disease. METHODS: A total of 78 patients with pneumomediastinum associated with DKA were identified in the literature search, and one patient treated in our hospital was included. The clinical features of the 79 patients were retrospectively analysed, and the pathogenesis, clinical symptoms, diagnostic methods, treatment strategies and prognoses were explored. RESULTS: All cases were confirmed by chest CT (computed tomography), and Kussmaul respiration, severe vomiting, chest pain were common symptoms. The main treatment principle was to correct acidosis and treat the primary disease. The majority of patients recovered within 1-2 weeks, and only 2 patients died. CONCLUSION: Pneumomediastinum associated with DKA is a rare disease, and it has a benign course when an early diagnosis is made and aetiological treatment is administered.

12.
Infect Drug Resist ; 13: 2277-2284, 2020.
Artículo en Inglés | MEDLINE | ID: mdl-32765003

RESUMEN

OBJECTIVE: To investigate the safety and efficacy of preoperative ultra-short-course chemotherapy, combined with surgical treatment for chest wall tuberculosis and summarize our experience in this regard, to provide a reference for national and international clinicians. METHODS: A retrospective analysis was conducted of the clinical data, preoperative anti-tuberculosis duration, and postoperative recurrence rate in 263 patients with chest wall tuberculosis spanning 5 years. RESULTS: Overall, 263 patients were treated with anti-tuberculosis drugs for about ± 12.49 days during the preoperative period. Simple chest wall tuberculosis was treated for ± 5.87 days and composite chest wall tuberculosis for ± 5.11 days. The postoperative recurrence rate of chest wall tuberculosis was 3.80%, which was close to or lower than the recurrence rate of routine preoperative anti-tuberculous therapy in patients subjected to ultra-short-range anti-tuberculosis treatment before surgery. CONCLUSION: Preoperative ultra-short-course chemotherapy combined with surgical treatment of chest wall tuberculosis did not increase the recurrence rate of chest wall tuberculosis; moreover, it could effectively shorten hospitalization time and improve patient compliance. Full-line anti-tuberculosis treatment and complete resolution of tuberculosis infections are crucial to curing chest wall tuberculosis.

13.
Artif Cells Nanomed Biotechnol ; 47(1): 2091-2097, 2019 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-31131637

RESUMEN

In previous studies, numerous dysregulated lncRNAs were identified using RNA-sequencing. Lung cancer is the most common malignant tumour worldwide and the second leading cause in cancer. The aim of this study is to investigate the function and mechanism of lincRNA00858 in the lung cancer. RT-PCR was used to detect the expression of lincRNA00858. Proliferation, invasion, and epithelial-mesenchymal transition (EMT) were examined by CCK8, transwell assay and western blot to evaluate the function of linc00858. Dual-luciferase reporter assay was used to identified the potential target of linc00858. Over-expression of linc00858 significantly promoted cell proliferation, invasion. We also found that linc00858 facilitated the EMT process. Dual-luciferase reporter assay revealed that linc00858 can bind with miR-3182 directly. Linc00858 can negatively regulate the expression of miR-3182. Further experiments demonstrated that MMP2 was the direct target of miR-3182. Rescue experiments revealed that linc00858 functioned through miR-3182/MMP2 axis. Taken together, we verified the role of an unknown linc00858 in lung cancer and provided its mechanism. Mechanistically, linc00858 acted as a competitive endogenous RNA to sponged miR-3182 and regulate MMP2 in lung cancer. Our study provided new clues for understanding the mechanism of lung cancer.


Asunto(s)
Progresión de la Enfermedad , Neoplasias Pulmonares/patología , Metaloproteinasa 2 de la Matriz/genética , MicroARNs/genética , ARN Largo no Codificante/genética , Secuencia de Bases , Línea Celular Tumoral , Movimiento Celular/genética , Proliferación Celular/genética , Transición Epitelial-Mesenquimal/genética , Humanos
14.
ACS Omega ; 4(4): 6775-6783, 2019 Apr 30.
Artículo en Inglés | MEDLINE | ID: mdl-31459799

RESUMEN

Herein, we present a facile method for deoxygenative hydroboration of a broad range of carboxylic acids under very mild conditions. The most striking feature of this attractive hydroboration is that this elusive and challenging transformation was realized without catalyst and solvent. The investigation of solvent effect showed that tetrahydrofuran was also suitable for this kind of reaction. Moreover, a successful gram-scale trial may provide a very promising toolkit for carboxylic acid reduction at a large scale.

15.
Artículo en Inglés | MEDLINE | ID: mdl-29128751

RESUMEN

Silver-containing lanthanum metaniobate Ag0.5La0.5Nb2O6 nanoparticles were synthesized by sol-gel polymerized complex method. A typical defect-perovskite structure was confirmed by XRD Rietveld refinements. The surface characteristics of the sample were tested by SEM, TEM and EDS measurements. SEM and TEM show that the sample presents ball-like particles with the diameters of 100nm to 400nm. The sample shows both self-activated luminescence and photocatalytic activities. Ag0.5La0.5Nb2O6 has a direct transition with band energy of 2.85eV. The Ag4d-O2p hybridization in the valence band contributes to the narrowed band gap. The luminescence properties of Ag0.5La0.5Nb2O6 have been investigated for the first time. The luminescence is characterized by two emission centers with maximum wavelength near 460 and 530nm. The emission and excitation spectra, decay curves and the thermal quenching mechanism were discussed. Ag0.5La0.5Nb2O6 shows the efficient photocatalytic activities and the photodegradation rate for methylene blue dye (MB) can reach about 95% under visible light (>420nm) irradiation in 5h. The trapped experiments for the active species were tested and discussed, which verified that OH radicals could be the major active species in photocatalysis.

16.
Org Lett ; 19(13): 3382-3385, 2017 07 07.
Artículo en Inglés | MEDLINE | ID: mdl-28644031

RESUMEN

It was found that homoleptic cyclopentadienyl lanthanide complexes Cp3Ln (Ln = Y (1), Yb (2), Sm (3), Nd (4), La (5), Cp = cyclopentadienyl) can be employed as excellent catalysts for the hydroboration of various aldehydes and ketones toward pinacolborane. These robust lanthanide catalysts exhibited high reactivity with low catalyst loadings (0.01-1 mol %) under mild conditions and good functional group tolerability. These complexes also demonstrated uniquely carbonyl-selective hydroboration in the presence of alkenes and alkynes.

17.
Dalton Trans ; 44(46): 20075-86, 2015 Dec 14.
Artículo en Inglés | MEDLINE | ID: mdl-26529326

RESUMEN

Reduction reactions of bis(ß-diketiminate)lanthanide(III) chlorides formed in situ by reactions of anhydrous LnCl3 with 2 equiv. of sodium salt of the ß-diketiminate ligand in THF with a Na/K alloy afforded a series of bis(ß-diketiminate)lanthanide(II) complexes LnL2(THF)n (L = L(2,6-Me2) = [N(2,6-Me2C6H3)C(Me)]2CH(-), n = 1, Ln = Eu (1); L = L(2,4,6-Me3) = [N(2,4,6-Me3C6H2)C(Me)]2CH(-), n = 1, Ln = Eu (2); L = L(2,6-iPr2) = [N(2,6-(i)Pr2C6H3)C(Me)]2CH(-), n = 0, Ln = Eu (3), Sm (4); L = L(2,6-ipr2)(Ph) = [(2,6-(i)Pr2C6H3)NC(Me)CHC(Me)N(C6H5)](-), n = 0, Ln = Eu (5), Yb (6); L = L(2-Me) = [N(2-MeC6H4)C(Me)]2CH(-), n = 1, Ln = Yb (7)) in high yields. All the complexes, especially the complexes of Sm(II) (4) and Eu(II) (5), were found to be excellent pre-catalysts for catalytic addition of amines to carbodiimides to multi-substituted guanidines with a wide scope of substrates. The activity depends both on the central metals and the ligands with the active sequence of Yb(II) < Eu(II) and Eu(II) < Sm(II) and L(2,6-Me2) < L(2,4,6-Me3) ∼ L(2,6-iPr2) < L(2,6-ipr2)(Ph) for the ligands. The mechanistic study by the isolation of guanidinate species and their reactivity revealed that Eu(II) monoguanidinate complexes Eu(L(2,6-Me2))[(C6H5N)C(NHCy)(NCy)](DME) (8) and Eu(L(2,6-ipr2)Ph)[(C6H5N)C(NHCy)(NCy)](THF)2 (9) should be the key active intermediates for the systems with Eu(II) complexes and a Yb(III) bis(guanidinate) complex Yb(L(2-Me))[(C6H5N)C(NHCy)(NCy)]2 (11) for the system using a Yb(II) complex.

18.
Dalton Trans ; 43(14): 5586-94, 2014 Apr 14.
Artículo en Inglés | MEDLINE | ID: mdl-24549149

RESUMEN

The readily accessible dianionic ß-diketiminato lanthanide amido complexes LnLN(SiMe3)2(THF) (L = {(2,6-(i)Pr2C6H3)NC(CH2)CHC(CH3)N(2,6-(i)Pr2C6H3)}(2-)) show an unprecedented reactivity toward carbodiimides. The reaction with N,N'-dicyclohexylcarbodiimide (DCC) led via [4 + 2] cycloaddition to γ-amidine-functionalized dianionic ß-diketiminato lanthanide amido complexes, LnL(1)N(SiMe3)2 (L(1) = {[(NHC6H11)(NC6H11)C]HC[C(CH2)N(2,6-(i)Pr2C6H3)]2}(2-), Ln = Sm(1), Yb(2), Y(3), Gd(4)). Conversion of a mixture of SmLN(SiMe3)2(THF) and NaN(SiMe3)2 with carbodiimide furnished the heterobimetallic complexes of Sm/Na with a novel amidinate-functionalized trianionic ß-diketiminate ligand, [Na(DME)2](µ-L(2))[SmN(SiMe3)2] (L(2) = {[C(N(i)Pr)2]HC[C(CH2)N(2,6-(i)Pr2C6H3)]2}(3-), DME = dimethoxyethane) (5) for N,N'-diisopropylcarbodiimide (DIC) and [Na(DME)3](+)[SmL(3)N(SiMe3)2](-) (L(3) = {[C(NCy)2]HC[C(CH2)N(2,6-(i)Pr2C6H3)]2}(3-)) (6) for DCC. Molecular structures of complexes 1-6 were determined by an X-ray single crystal structure analysis. Complexes 1-4 were found to be highly active initiators of the ring-opening polymerization (ROP) of L-lactide (L-LA). The activity depended on the central metal with the increasing sequence of Yb < Y < Gd < Sm. Notably, the binary 1/BnOH (benzyl alcohol) system exhibited an "immortal" nature and proved able to convert 2000 equivalents of L-LA with up to 100 equivalents of BnOH per initiator. All the polylactides (PLAs) obtained showed monomodal, narrow molar mass distributions (M(w)/M(n) = 1.08-1.13) with the M(n) (average number molar mass) decreasing with increasing amount of BnOH proportionally.

19.
Dalton Trans ; 42(16): 5890-901, 2013 Apr 28.
Artículo en Inglés | MEDLINE | ID: mdl-23459864

RESUMEN

Various lanthanide aryloxide complexes supported by bridged bis(amidinate) ligand L, LLnOAr(DME) (L = Me3SiNC(Ph)N(CH2)3NC(Ph)NSiMe3, DME = dimethoxyethane, Ln = Y, Ar = 2,6-(Me)2C6H3 (1), 2,6-((i)Pr)2C6H3 (2), 2,6-((t)Bu)2-4-(Me)C6H2 (3); Ar = 2,6-((t)Bu)2-4-(Me)C6H2, Ln = Nd (4), Sm (5), Yb (6)) were synthesized, and complexes 1, 2 and 4­6 were characterized by single crystal X-ray diffraction. All the complexes are efficient precatalysts for catalytic addition of amines to carbodiimides. The catalytic activity is influenced by lanthanide metals and the aryloxide groups (Nd (4) Sm (5) < Y (3) Yb (6) and -2,6-(Me)2C6H3 < -2,6-((i)Pr)2C6H3 < -2,6-((t)Bu)2-4-(Me)C6H2). The catalytic addition reaction with 3 showed a good scope of substrates. The mechanism investigation revealed the real active intermediate being the monoguanidinate complexes supported by an aryloxide and an amidine-functionalized amidinate group, L'Ln[O2,6-((t)Bu)2-4-(Me)C6H2][RNCNHRN(Ar')] (L' = Me3SiNHC(Ph)N(CH2)3NC(Ph)NSiMe3, R = (i)Pr, Ar' = phenyl, Ln = Yb (8), Y (11); R = Cy, Ar' = phenyl, Ln = Yb (10), Y (12); R = (i)Pr, Ar' = 4-ClC6H4, Ln = Yb (9)), which were isolated from the reactions of 6 (or 3) with amine and carbodiimide in a molar ratio of 1:1:1 and structurally characterized. The Ln-active group in the present precatalyst is a Ln­amidinate species, not the Ln­OAr group.

20.
Dalton Trans ; 42(19): 7009-18, 2013 May 21.
Artículo en Inglés | MEDLINE | ID: mdl-23511958

RESUMEN

Reaction of LnCl3 with a lithium salt of bridged bis(guanidinate) bearing a rigid naphthalene linker [Li2{LH2}2Li2] (LH2 = 1,8-C10H6{NC(N(i)Pr)(NH(i)Pr)}2) (1), which was synthesized by the reaction of 1,8-diaminonaphthalene with 2 equiv. of (n)BuLi, followed by treatment with 2 equiv. of N,N'-diisopropylcarbodiimide, yielded the chlorides [LnCl{LH2}] (Ln = Yb (2), Y (3)) in good yields. Metathesis reaction of 2 and 3 with NaN(SiMe3)2 did not afford the corresponding amide complexes, but the deprotonation products of [Ln{LH}]2 (LH = 1,8-C10H6{NC(N(i)Pr)(NH(i)Pr)}{NC(N(i)Pr)2}; Ln = Yb (4), Y (5)) were isolated instead. The LH in 4 and 5 both act as a bridging ligand binding to two metals in a µ-η(1):η(2):η(2) fashion, and the re-arrangement of LH occurred during the reaction. The size of the amido group was found to have a great influence on the outcome of the metathesis reaction. Reaction of 2 with bulky NaNH(C6H3(i)Pr2-2,6) afforded 4 as the only product, whereas the same reaction with less bulky LiNH(C6H4Cl-4) and LiNH(C6H4CH3-4) led to the corresponding amides, [Yb{LH2}(NHC6H4Cl-4)]2 (6) and [Yb{LH2}(NHC6H4CH3-4)]2 (7), respectively. The re-arrangement of ligands was also observed in both cases. A possible pathway for the deprotonation of LH2 was discussed. Molecular structures of 1-7 were determined by X-ray single crystal analysis.

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