Regioselective Synthesis of N2-Alkylated-1,2,3 Triazoles and N1-Alkylated Benzotriazoles: Cu2S as a Recyclable Nanocatalyst for Oxidative Amination of N, N-Dimethylbenzylamines.

Copper chalcogenide nanoparticles (Cu2S) synthesized for the first time from a single-source precursor, CuSPh, act as highly efficient and reusable heterogeneous catalyst for regioselective amination of N, N-dimethylbenzylamines with various azoles. The reaction involves N-H/C-H cross-dehydrogenative coupling (CDC) and demonstrates wide functional group tolerance. It provides highly selective access to N1-alkylated benzotriazoles, N2-alkylated 1,2,3-triazoles and 4-phenyl-1,2,3-triazoles, and N-alkylated carbazoles in 70-89% yields under solvent-free conditions. The Cu2S nanocatalyst has been characterized by PXRD, XPS, SEM-EDX, and HR-TEM analysis. Mechanistic studies suggest that the reaction follows a radical pathway and involves an iminium ion intermediate.

Cranial Autonomic Symptoms in Migraine: An Observational Study.

Objective: Our aim was to observe frequency of cranial autonomic symptoms (CAS) in migraineurs (primary) and its relation with laterality of headache or other factors, if any. Background: Migraine episodes have headaches with or without aura, and sometimes associated with systemic autonomic nervous system symptoms. Primarily presence of cranial autonomic symptoms suggests diagnosis of TACs. But many studies reported cranial autonomic symptoms (CAS) ranging from 26% to 80% in migraine patients. Material and Methods: Consecutive patients of migraine attending our headache clinic were included in our study. Presence of CAS was recorded with respect to ocular, nasal, facial and aural symptoms along with headache characteristics and laterality information. Detailed clinical examination was performed. We used ICHD 3 (beta version) criteria. Results: Our study cohort comprised of 200 patients having mean (± SD) age 31.12 (± 10.67) years. There were 157 (78.5%), females. Out of 200 patients, 148 (74%) were having at least one CAS, of which 70% were having 2 or more CAS. Frequency of CAS was lacrimation (45.5%), conjunctival injection (34.5%), eyelid edema (34%), aural fullness (27.5%), facial sweating (25%), facial flushing (17.5%), nasal congestion (9%), rhinorrhea (5%) and ptosis (4%). Bilateral CAS was present in 129 (87%) and unilateral CAS in 19 (13%) (OR 35.31; 95% CI 9.19 to 135.7), (P < 0.0001). Sunlight as a trigger was present in all 148 (100%) patients. Conclusion: Our study showed that CASs in migraine is common and bilateral. Sunlight triggers headache in almost all CAS positive patients.

Catalytically active nanosized Pd9Te4 (telluropalladinite) and PdTe (kotulskite) alloys: first precursor-architecture controlled synthesis using palladium complexes of organotellurium compounds as single source precursors.

Several intermetallic binary phases of Pd-Te including Pd3Te2, PdTe, PdTe2, Pd9Te4, Pd3Te, Pd2Te, Pd20Te7, Pd8Te3, Pd7Te2, Pd7Te3, Pd4Te and Pd17Te4 are known, and negligible work (except few studies on PdTe) has been done on exploring applications of such phases and their fabrication at nanoscale. Hence, Pd(ii) complexes Pd(L1)Cl2 and Pd(L2-H)Cl (L1): Ph-Te-CH2-CH2-NH2 and L2: HO-2-C6H4-CH[double bond, length as m-dash]N-CH2CH2-Te-Ph were synthesized. Under similar thermolytic conditions, complex Pd(L1)Cl2 with bidentate coordination mode of ligand provided nanostructures of Pd9Te4 (telluropalladinite) whereas Pd(L2-H)Cl with tridentate coordination mode of ligand yielded PdTe (kotulskite). Bimetallic alloy nanostructures possess high catalytic potential for Suzuki coupling of aryl chlorides, and reduction of 4-nitrophenol. They are also recyclable upto six reaction cycles in Suzuki coupling.

Catalysis with magnetically retrievable and recyclable nanoparticles layered with Pd(0) for C-C/C-O coupling in water.

Nanoparticles layered with palladium(0) were prepared from nano-sized magnetic Fe3O4 by coating it with silica and then reacting sequentially with phenylselenyl chloride under an N2 atmosphere and palladium(ii) chloride in water. The resulting Fe3O4@SiO2@SePh@Pd(0) NPs are magnetically retrievable and the first example of NPs in which the outermost layer of Pd(0) is mainly held by selenium. The weight percentage of Pd in the NPs was found to be 1.96 by ICP-AES. The NPs were authenticated via TEM, SEM-EDX, XPS, and powder XRD and found to be efficient as catalysts for the C-O and C-C (Suzuki-Miyaura) coupling reactions of ArBr/Cl in water. The oxidation state of Pd in the NPs having size distribution from ∼12 to 18 nm was inferred as zero by XPS. They can be recycled more than seven times. The main features of the proposed protocols are their mild reaction conditions, simplicity, and efficiency as the catalyst can be separated easily from the reaction mixture by an external magnet and reused for a new reaction cycle. The optimum loading (in mol% of Pd) was found to be 0.1-1.0 and 0.01-1.0 for O-arylation and Suzuki-Miyaura coupling, respectively. For ArCl, the required amount of NPs was more as compared to that needed for ArBr. The nature of catalysis is largely heterogeneous.

Graphene oxide supported cobalt phosphide nanorods designed from a molecular complex for efficient hydrogen evolution at low overpotential.

Thermolysis of molecular inorganic complex [CoCl2(PPh3)2] has resulted in uniform Co2P nanorods which on grafting on graphene oxide exhibit ultra high hydrogen evolution activity with a cathodic current density of 100 mA cm-2 at an overpotential of 154 mV and excellent stability for at least 70 h.

Solvent-tailored Pd3P0.95 nano catalyst for amide-nitrile inter-conversion, the hydration of nitriles and transfer hydrogenation of the C[double bond, length as m-dash]O bond.

For the first time, a one pot thermolysis of [Pd(PPh3)2Cl2] prepared by reacting Ph3P with PdCl2 in a 2 : 1 molar ratio in MeOH at 280 °C in a trioctylphosphine (TOP) and oleylamine(OA)-octadecane(ODE) mixture (1 : 1) was used to prepare quantum dots (QDs; size ∼2-3 nm) and nanoparticles (NPs; size ∼13-14 nm), respectively, of composition Pd3P0.95. TEM, SEM-EDX, powder-XRD and XPS (for QDs only) were used to authenticate the two nanophases. 31P{1H}NMR experiments performed to monitor the progress of thermolysis reactions revealed that the phosphorus present in the Pd3P0.95 QDs had come from TOP, whereas in Pd3P0.95 NPs, its source is triphenylphosphine. The nature of the solvent did not affect the chemical composition of the nano-phase but controlled its size. Probably, solvent dependent, unique, single source precursors (SSPs) of palladium were generated in situ, and controlled the size. The catalytic activity of both Pd3P0.95 QDs and NPs was explored. The QDs were found to be efficient as a catalyst for the amide-nitrile interconversion at room temperature (yield up to 92% in 4 h), hydration of nitriles and transfer hydrogenation (TH) of carbonyl compounds with yields up to 96% in 3-4 h. The yields and reaction rates of amide-nitrile inter-conversion and TH when catalyzed by Pd3P0.95 QDs were found to be higher compared to the ones observed with the Pd/C catalyst. The binding energy of Pd(3d) in the X-ray photoelectron spectrum (XPS) of Pd3P0.95 indicated an electron transfer from the metal to phosphorus, resulting in electron deficient palladium, which facilitates the coordination of a substrate to Pd and drives the reaction. The reusability of Pd3P0.95 QDs for the interconversion was found to be up to 4-times, while for the transfer hydrogenation of carbonyl compounds it was up to 6-times, but with a diminished yield. Pd3P0.95 NPs were found to be less active (yield up to 36% in optimized reaction conditions) in comparison to Pd3P0.95 QDs. The mercury poisoning test suggested that the catalysis predominantly proceeded heterogeneously on the surface of the QDs. The PXRD and XPS results did not suggest a significant variation in the phase of QDs after the third catalytic cycle. The bleeding of Pd during catalysis (determined by flame AAS) and the agglomeration of QDs as supported by the SEM-EDX and TEM results are probably responsible for the reduction in the catalytic activity of QDs after reusing three times.

Oxidative C-C bond formation and C-N bond cleavage catalyzed by complexes of copper(i) with acridine based (E N E) pincers (E = S/Se), recyclable as a catalyst.

Copper(i) complexes of 4,5-bis((phenylthio/seleno)methyl)acridine, [CuLBr] (C1 and C2) (L = L1/L2; pincer type (E N E) ligand), were synthesized and found to be thermally stable, and moisture and air insensitive. The complexes and ligands were characterized by multinuclei NMR and single crystal X-ray diffraction. In both complexes C1 and C2, ligands L1 and L2 coordinate with Cu in a pincer mode furnishing two six-membered chelate rings, with the distorted tetrahedral geometry of donor atoms around Cu. The Cu-S and Cu-Se bond lengths (Å) are 2.2482(17)-2.2979(16) and 2.3603(14)-2.4177(13) respectively. These complexes served as efficient catalysts for cross dehydrogenative coupling of unactivated tertiary amines with unactivated terminal alkynes, and cleavage of the benzylic (C-N) bond of N,N dimethylbenzylamines under oxidative solvent-free conditions. The reactions were found to be highly selective, and no over-oxidation to acid was observed. A low catalytic loading of 1.0 mol% was good enough to bring about both these transformations with recyclability up to five times.

Ultra-small palladium nano-particles synthesized using bulky S/Se and N donor ligands as a stabilizer: application as catalysts for Suzuki-Miyaura coupling.

Two chalcogenated ligands L1 and L2 containing anthracene core and amine functionality have been synthesized. Both the ligands have been characterized using 1H and 13C{1H} NMR techniques. The structure of L1 has also been corroborated by single crystal X-ray diffraction. Application of L1 and L2 as stabilizers for palladium nano-particles (NPs) has been explored and six different types of NPs 1-6 have been prepared by varying the quantity of stabilizer. The nano-particles have been characterized by PXRD, EDX, and HRTEM techniques. The size of NPs has been found to be in the range of ∼1-2 nm, 2-3 nm, 4-6 nm, 1-2 nm, 1-2 nm and 3-5 nm for 1-6 respectively. The catalytic activities of 1-6 have been explored for Suzuki-Miyaura coupling of phenyl boronic acid with various aryl halides. These NPs showed good catalytic activity for various aryl chlorides/bromides at low catalyst loading (5 mg). Among 1-6, the highest activity has been observed for NPs 1, probably due to their relatively small size and high uniformity in the dispersion. The recyclability of the NPs upto 5 catalytic cycles is a distinct advantage.

Base free N-alkylation of anilines with ArCH2OH and transfer hydrogenation of aldehydes/ketones catalyzed by the complexes of η5-Cp*Ir(iii) with chalcogenated Schiff bases of anthracene-9-carbaldehyde.

The condensation of anthracene-9-carbaldehyde with 2-(phenylthio/seleno)ethylamine results in Schiff bases [PhS(CH2)2C[double bond, length as m-dash]N-9-C14H9](L1) and [PhSe(CH2)2C[double bond, length as m-dash]N-9-C14H9] (L2). On their reaction with [(η5-Cp*)IrCl(µ-Cl)]2 and CH3COONa at 50 °C followed by treatment with NH4PF6, iridacycles, [(η5-Cp*)Ir(L-H)][PF6] (1: L = L1; 2: L = L2), result. The same reaction in the absence of CH3COONa gives complexes [(η5-Cp*)Ir(L)Cl][PF6] (3-4) in which L = L1(3)/L2(4) ligates in a bidentate mode. The ligands and complexes were authenticated with HR-MS and NMR spectra [1H, 13C{1H} and 77Se{1H} (in the case of L2 and its complexes only)]. Single crystal structures of L2 and half sandwich complexes 1-4 were established with X-ray crystallography. Three coordination sites of Ir in each complex are covered with η5-Cp* and on the remaining three, donor atoms present are: N, S/Se and C-/Cl-, resulting in a piano-stool structure. The moisture and air insensitive 1-4 act as efficient catalysts under mild conditions for base free N-alkylation of amines with benzyl alcohols and transfer hydrogenation (TH) of aldehydes/ketones. The optimum loading of 1-4 as a catalyst is 0.1-0.5 mol% for both the activations. The best reaction temperature is 80 °C for transfer hydrogenation and 100 °C for N-alkylation. The mercury poisoning test supports a homogeneous pathway for both the reactions catalyzed by 1-4. The two catalytic processes are most efficient with 3 followed by 4 > 1 > 2. The mechanism proposed on the basis of HR-MS of the reaction mixtures of the two catalytic processes taken after 1-2 h involves the formation of an alkoxy and hydrido species. The real catalytic species proposed in the case of iridacycles results due to the loss of the Cp* ring.

GO-Cu7S4 catalyzed ortho-aminomethylation of phenol derivatives with N,N-dimethylbenzylamines: site-selective oxidative CDC.

Copper chalcogenide nanoparticles (Cu7S4) supported on graphene oxide (GO) have been synthesized for the first time from Cu2S, and used as highly efficient heterogeneous catalysts for oxidative ortho-selective C-H aminomethylation of phenols with N,N-dimethylbenzylamines. The NPs (30-80 nm) have been characterized by HRTEM, SEM-EDX, PXRD, FTIR, Raman, ICP-AES and XPS analyses. The NP catalyzed sp2-sp3 cross dehydrogenative coupling (CDC) features a broad substrate scope, excellent functional group tolerance, high yields, use of an inexpensive and reusable copper catalyst, mild conditions, and no need for pre-functionalization of substrates.

Palladium(ii) complexes of N,N-diphenylacetamide based thio/selenoethers and flower shaped Pd16S7 and prismatic Pd17Se15 nano-particles tailored as catalysts for C-C and C-O coupling.

2-Bromo-N,N-diphenylacetamide (P1) prepared by reacting diphenylamine with α-bromoacetyl bromide, on treatment with Na2S and Na2Se generated in situ, has resulted in thio and selenoether ligands, L1 ((Ph2NCOCH2)2S) and L2 ((Ph2NCOCH2)2Se), respectively. Reacting these ligands with Na2PdCl4 in ethanol at room temperature resulted in their complexes [Pd(L1/L2)2Cl2] (C1/C2). P1, L1, L2, C1 and C2 were characterized by 1H, 13C{1H} and 77Se{1H} NMR spectroscopy, IR spectroscopy and High resolution mass spectrometry (HR-MS). Single crystal structures of all the five compounds were determined by X-ray diffraction. In both C1 and C2 the geometry of Pd is nearly square planar. Flower shaped Pd16S7 (size 26-50 nm) and prismatic Pd17Se15 NPs (size 20-55 nm) were synthesized by a single source precursor route (thermolysis at ∼280 °C in trioctylphosphine) from air and moisture insensitive C1 and C2, respectively. These shapes of the two nanophases were unknown hitherto. They were characterized by powder X-ray diffraction (PXRD), SEM-EDX and HR-TEM and found to show good catalytic activity for Suzuki-Miyaura (Pd loading 0.5 mol%; yield up to 96%) and C-O (Pd loading 0.5 mol%; yield up to 96%) coupling reactions (at 100 °C) of aryl bromides with phenylboronic acid and phenol, respectively. The complexes C1 and C2 were found very efficient for Suzuki-Miyaura and C-O coupling as revealed by their optimum loading of 0.0001-0.01 and 0.1 mol% of Pd, respectively, for the two reactions. The reuse of the complexes or NPs as a catalyst is demonstrated.

Trinuclear complexes of palladium(ii) with chalcogenated N-heterocyclic carbenes: catalysis of selective nitrile-primary amide interconversion and Sonogashira coupling.

3-Methyl-1-(2-(phenylthio/seleno)ethyl)-1H-benzo[d]imidazol-3-ium iodide (L1/L2), a precursor of sulfated/selenated N-heterocyclic carbene, was synthesized by the reaction of benzimidazole with 1,2-dichloroethane followed by treatment with PhS/SeNa and MeI. The reaction of L1/L2 with Ag2O followed by treatment with [Pd(CH3CN)2Cl2] (metal to ligand ratio 3 : 2), i.e. transmetallation, resulted in trinuclear palladium(ii) complexes [Pd3(L1/L2-HI)2(CH3CN)Cl6] (1-2). The complexes were characterized with 1H, 13C{1H} and 77Se{1H} NMR (2 only), elemental analyses, HR-MS and single-crystal X-ray diffraction. The geometry of three Pd atoms in each complex is nearly square planar. The Pd-S/Se, Pd-C, Pd-N and Pd-Cl bond distances (Å) in 1/2 are 2.3179(19)/2.4312(10), 1.968(7)/1.952(4), 2.073(8)/2.079(4) and 2.2784(19)-2.298(2)/2.292(2)-2.3003(15), respectively. In both the complexes, all Cl are trans to each other. For the central Pd atom, two benzimidazole rings are also trans to each other. The C-HCl non-covalent interactions result in a three-dimensional network. The moisture and air insensitive trinuclear Pd(ii) complexes 1 and 2 are thermally stable and efficient as a catalyst for nitrile-amide interconversion and amine-free Sonogashira C-C coupling (in the presence of CuI). The optimum temperature is 80 °C for the interconversion and 110 °C for the coupling. The catalytic protocols are applicable to both aliphatic and aromatic amides/nitriles. The optimum catalyst loading is 1 mol% for the C-C coupling and 0.5 to 1 mol% for the interconversion. K2CO3 as a base gives the best result for Sonogashira C-C coupling. In the conversion of nitriles to amides, the formation of an acid was not detected. After using once, 1/2 can carry out the conversion of ten fresh lots of nitriles to amides with almost the same efficiency. The real catalytic species for the interconversion and coupling appear to be based on Pd(ii) and Pd(0), respectively.

Reusable Catalyst for Transfer Hydrogenation of Aldehydes and Ketones Designed by Anchoring Palladium as Nanoparticles on Graphene Oxide Functionalized with Selenated Amine.

The treatment of graphene oxide with ClCH2COOH, thionyl chloride, and 2-(phenylselenyl)ethylamine successively has resulted in functionalization of its surface with selenated ethylamine molecules which may act as chelating (Se, N) ligands. The graphene oxide grafted with (Se, N) donor sites (GO-Se) on treatment with Na2PdCl4 and NaOH gave GO-Se anchored with Pd(0) nanoparticles (NPs) (GO-Se-Pd). The X-ray diffraction (powder), FT-IR, XPS, Raman spectroscopy, thermogravimetric analysis (TGA), and electron microscopic techniques (SEM and HR-TEM) authenticated the formation of GO-Se-Pd. The distribution of Pd(0) NPs of size ∼1-3 nm on GO-Se was found nearly uniform. The transfer hydrogenation of carbonyl compounds (aldehydes/ketones) with 2-propanol was catalyzed with GO-Se-Pd. The catalyst equivalent to 0.25 mol % of Pd was sufficient to convert aldehydes and ketones to alcohols in good yield (nearly quantitative for some substrates) and found somewhat more efficient for aldehydes than ketones. The reusability of GO-Se-Pd studied for transfer hydrogenation of 4-anisaldehyde to the corresponding alcohol can be understood by ∼96% conversion even in the sixth catalytic run. Flame AAS analysis of GO-Se-Pd revealed negligible leaching of Pd even after the sixth catalytic reaction cycle. Hot filtration experiments suggested the heterogeneous nature of the catalyst.

Palladacycles of sulfated and selenated Schiff bases of ferrocene-carboxaldehyde as catalysts for O-arylation and Suzuki-Miyaura coupling.

Schiff base ligands (L1: sulfated and L2: selenated) having a ferrocene core synthesized by reacting ferrocene-carboxaldehyde with 2-(phenylthio/seleno)ethylamine on treatment with Na2PdCl4 in the presence of NaOAc give cyclopalladated complexes [Pd(L1/L2-H)Cl] (1/2). Complex 1 of a sulfated Schiff base L1, on reacting with one equivalent of triphenylphosphine gives complex [Pd(L1-H)PPh3Cl] (3), formed due to cleavage of a Pd-S bond. With 2 such a reaction does not occur, as a Pd-Se bond being stronger than that of its sulfur analogue does not get cleaved. L1, L2 and their complexes 1-3 were authenticated with HR-MS, 1H, 13C{1H} and 77Se{1H} NMR spectroscopy. The single crystal structures of 1-3 were determined with X-ray diffraction. Palladium in all three complexes has nearly a square planar geometry. The Pd-S, Pd-Se and Pd-P bond distances are 2.4249(12), 2.5058(14) and 2.2445(17) Šrespectively. The catalytic activity of complexes 1-3 was explored for O-arylation of phenol and Suzuki-Miyaura coupling (SMC) of phenylboronic acid with aryl bromides and chlorides. The optimum reaction time for SMC of ArBr is 3 h whereas for ArCl it is 6 h. The TON values of O-arylation catalyzed with complexes 1-3 are up to ∼170 (TOF, 28 h-1) and SMC ∼9300 (TOF, 3100 h-1) for the reaction time of the order of 3 and 6 h respectively. The catalytic process is somewhat more efficient with 2 (Pd bonded with a selenoether group), than 3, followed by 1.

Stroke Associated With Varicella Zoster Vasculopathy: A Clinicoradiological Profile of 3 Patients.

INTRODUCTION: Varicella zoster (VZ) vasculopathy is a rare but well recognized cause of stroke. In the absence of zoster rash and infection in remote past, the disease can pose diagnostic challenge. We report 3 cases of anterior circulation stroke occurring in close temporal relation to VZ. Their clinical, radiologic, and angiographic features are discussed. CASE REPORT: Of the 3 patients, 2 had stroke within a span of 4 to 6 weeks of herpes zoster ophthalmicus while the third patient had zoster of cervical dermatome. Magnetic resonance imaging revealed acute subcortical infarcts in 2, while 1 patient showed acute on chronic infarct in left middle cerebral artery territory. The magnetic resonance angiography was abnormal in 2 patients while it was normal in third. All the patients were treated with acyclovir and antiplatelets with good recovery in 2. CONCLUSIONS: VZ associated vasculopathy may have diverse clinical profile and neuroimaging features. It should be considered as an important and treatable cause of stroke in appropriate clinical settings.

Complexes of (η5-Cp*)Ir(iii) with 1-benzyl-3-phenylthio/selenomethyl-1,3-dihydrobenzoimidazole-2-thione/selenone: catalyst for oxidation and 1,2-substituted benzimidazole synthesis.

The treatment of 1-benzyl-3-phenylthio/selenomethyl-1,3-dihydrobenzoimidazole-2-thione/selenone [L1-L4] with [(η5-Cp*)IrCl(µ-Cl)]2 at 25 °C followed by NH4PF6 results in [(η5-Cp*)Ir(L)Cl][PF6] (1-4 for L = L1 to L4), authenticated with high-resolution mass spectrometry (HR-MS) and multi-nuclei nuclear magnetic resonance (NMR) imaging (1H, 13C{1H} and 77Se{1H}). The structures of 1-4, established with single-crystal X-ray diffraction, reveal a "piano-stool" geometry around the Ir. The Ir-thio/selenoether (Ir-S/Ir-Se) bond distances (Å) are 2.347(18)-2.355(4)/2.4663(12)-2.4663(13) and Ir-thione/selenone (Ir-S/Ir-Se) distances are 2.4146(19)-2.417(2)/2.5141(16)-2.5159(12). The reaction of 1,2-phenylenediamine with benzylic alcohols and furfuryl alcohol under mild and ambient conditions, catalyzed efficiently with complexes 1-4, generates bisimine in situ. Cyclization and rearrangement via 1,3-hydride shift triggered by its electrophilic activation with Ir(iii) species finally results in 1,2-disubstituted benzimidazole. The yield of the heterocycles in this one-pot synthesis is excellent to good. The aldehydes generated in situ by aerial oxidation of alcohols in the presence of 1-4 as catalysts are precursors to the bisimine as the protocols of this heterocycle synthesis carried out in the absence of 1,2-phenylenediamine give them in excellent-to-good yield. The oxidation of alcohols by hydrogen transfer to acetone was catalyzed efficiently with complexes 1-4 and resulted in aldehyde/ketone in excellent-to-good yield. Each catalytic process is marginally more efficient with 1 than its counterparts.

Sonogashira (Cu and amine free) and Suzuki coupling in air catalyzed via nanoparticles formed in situ from Pd(ii) complexes of chalcogenated Schiff bases of 1-naphthaldehyde and their reduced forms.

The reaction of 1-naphthaldehyde with 2-(phenylthio/seleno)ethylamine afforded air- and moisture-insensitive Schiff bases: C10H7-1-CH[double bond, length as m-dash]N-CH2CH2EPh (L1: E = S; L2: E = Se). Then, on treatment with NaOAc and Li2PdCl4, palladacycles, [Pd(L1-H/L2-H)Cl] (1/2) were formed at room temperature, in which L1/L2 are ligated as an unsymmetric (C-, N, E) pincer. The reduction of >C[double bond, length as m-dash]N bonds of L1 and L2 with sodium borohydride gave C10H7-1-CH2NH-CH2CH2EPh (L3: E = S; L4: E = Se). The reactions of L3/L4 at room temperature, similar to those of L1/L2, resulted in the formation of complex [Pd(L3/L4)Cl2] (3/4), in which the ligand is coordinated in a bidentate (N, E) mode. The yield of all the complexes was >85%. Characterization by HR-MS, 1H, 13C{1H} and 77Se{1H} NMR spectra of L1-L4 and their complexes 1-4 were performed. The structures of L1 and 1-4 were established with single-crystal X-ray diffraction. In all the complexes, the geometry of palladium was distorted square planar. The Pd-S bond distances in 1 and 3 were 2.426(12) and 2.259(2) Å, respectively, whereas Pd-Se bond lengths (Å) were 2.523(11) (2) and 2.369(10) (4) Å. The catalytic activities of 1-4 were explored for copper- and amine-free Sonogashira and Suzuki-Miyaura coupling (SMC) of aryl halides under aerobic conditions. The amount of catalyst required for achieving good conversion was 0.01 and 0.05 mol% for SMC and Sonogashira coupling, respectively. The conversion of some substrates reached a maximum in 1 and 2 h for Sonogashira coupling and SMC, respectively. The palladacycles as catalysts gave good conversion efficiency. The generation of palladium-containing nanoparticles (NPs) during both coupling reactions was observed. These were isolated and HR-TEM studies were performed on them and revealed their size as ∼2-7 nm. The SEM-EDX analysis indicated the presence of organochalcogen ligands or their fragments in the samples. They independently catalyzed both reactions. Therefore, the role of 1-4 in catalysis undoubtedly exists. For Sonogashira coupling, the formation and role of such Pd-based NPs under aerobic conditions were observed for the first time. The complexes 1-4 showed the potential for reuse, as in the eighth cycle, conversion dropped by only 20%.

Dopa-responsive Dystonia in a Child Misdiagnosed as Cerebral Palsy.

Dopa-responsive dystonia also known as "Segawa's syndrome" was first described in 1976. The dystonia typically shows diurnal variations and is more marked toward the end of the day and improves in sleep. This entity is often misdiagnosed in the clinical setting, mostly due to the lack of awareness, and these patients are exposed to various treatment regimens and nonpharmacological measures. We present a boy being treated as dystonic cerebral palsy who showed significant improvement in dystonic symptoms with L-dopa therapy.

'Click' generated 1,2,3-triazole based organosulfur/selenium ligands and their Pd(ii) and Ru(ii) complexes: their synthesis, structure and catalytic applications.

1-(2,6-Diisopropylphenyl)-4-(phenylthio/selenomethyl)-1H-1,2,3-triazole (L1/L2) was synthesized by a 'Click' reaction and treated with [Pd(CH3CN)2Cl2] for 5 h or [(η(6)-C6H6)RuCl(µ-Cl)]2 for 8 h (followed by reaction with NH4PF6) at room temperature, resulting in complexes [Pd(L)Cl2] (1 and 2) or [(η(6)-C6H6)Ru(L)Cl]PF6 (3 and 4) (L = L1 or L2), respectively. The four complexes (1-4) and ligands (L1 and L2) were characterized with (1)H, (13)C{(1)H} and (77)Se{(1)H} NMR spectroscopy and high resolution mass spectrometry. The single crystal structures of 1-4 were solved. The geometry of Pd in 1 and 2 is distorted square planar. The Pd-S and Pd-Se bond distances in 1 and 2 are 2.277(3) and 2.384(6) Å respectively. In 3 and 4, there is a pseudo-octahedral "piano-stool" type disposition of donor atoms around Ru. The Ru-S and Ru-Se bond lengths in 3 and 4 are 2.3728(12) and 2.4741(6) Å respectively. The catalytic activity of complexes 1 and 2 was explored for Suzuki-Miyaura coupling (SMC) in water and the Sonogashira coupling reaction. For various aryl bromides, including deactivated ones, complexes 1 and 2 were found to be efficient catalysts for both couplings. The optimum loading of 1 and 2 required to catalyze both coupling reactions is of the order of 0.001-2 mol% of Pd. For SMC, no additive or phase transfer catalyst was added. For catalysis of the transfer hydrogenation (TH) of aldehydes and ketones, the half-sandwich Ru(ii) complexes 3 and 4 were explored. Their optimum catalytic loading was found to be 0.1-0.4 mol% of Ru. For TH, both the water solvent and the glycerol hydrogen source are environmentally friendly. The catalytic efficiencies of 3 and 4 are comparable with those reported for other catalysts for TH carried out with 2-propanol or glycerol as a H-source. 1, with a sulfur ligand, is more efficient than 2 (Se analog) for both SMC and the Sonogashira coupling. The activities of 3 and 4 for TH are in the order Se > S.