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Journal of Chemical Sciences [Formerly: Proceedings (Chemical Sciences)] Vol. 124, No. 6, November 2012 CONTENTS Special issue on Modern Trends in Inorganic Chemistry (MTIC-XIV) Foreword ......................................................................... 1143 Mechanism of -O–O- bond activation and catalysis by RuIII-pac complexes (pac = polyaminocarboxylate) Debabrata Chatterjee. 1145–1150 Ru-pac (pac = polyaminocarboxylate) complex catalysed -O–O- bond t activation in H2O2, BuOOH and KHSO5 leading to the formation of various catalytically active species, viz. [RuIII(pac)(OOH)]2j, [RuIV(pac)(OH)]j and [RuV(pac)(O)]j, and their reactivity towards oxidation of cysteine and azo-dye. Helical chirality induction of expanded porphyrin analogues Jun-Ichiro Setsune . 1151–1163 Based on the fact that binding chiral ligands cause excess of unidirectional helical chirality in the cyclooctapyrrole O1 with 32p-cycloconjugation, helical chirality induction in the CuII complexes of cyclooctapyrrole O2 with interrupted p-conjugation and the dinuclear CoII complexes of cyclotetrapyrroletetrapyridine O3 is demonstrated. Organometallic complexes of the platinum metals: Synthesis, structure, and catalytic applications M = H, Cl M Piyali Paul and Samaresh Bhattacharya . 1165–1173 C H If an alkyl or aryl CjH bond of a judiciously chosen ligand is brought in close C proximity to a platinum metal-bound hydride or chloride by coordination I II through regular donor atoms (as in I), then facile activation of that CjH bond takes place leading to the formation of cyclometallated species (II). Digestive ripening: a synthetic method par excellence for core– shell, alloy, and composite nanostructured materials Srilakshmi P Bhaskar and Balaji R Jagirdar. 1175–1180 Solvated Metal Atom Dispersion method in combination with digestive ripening process is presented as a powerful synthetic method for realizing highly monodisperse metal, core–shell, alloy, and composite nanoparticles. Electronic structures of ruthenium complexes encircling non- innocent ligand assembly Amit Das, Dipanwita Das, Tanaya Kundu and Goutam Kumar Lahiri. 1181–1189 The sensitivity concerning the electronic structural aspects of the ruthenium complexes with non-innocent ligands (L) in accessible redox states could be convincingly addressed via the critical and collective analysis of crystal structures, magnetism, spectroelectrochemistry in combination with DFT calculations. 1137 1138 Contents Simple tertiary phosphines to hexaphosphane ligands: Syntheses, transition metal chemistry and their catalytic applications Maravanji S Balakrishna, Sowmya Rao and Bimba Choubey . 1191–1204 Studies on synthesis, transition metal chemistry and catalytic applications of several phosphorus-based ligands have been presented. Reactions of a stable dialkylsilylene and their mechanisms Mitsuo Kira . 1205–1215 Studies of the reactions of isolable dialkylsilylene 1 have revealed that the reaction modes are not limited to A bond insertion and : bond addition but more diversified including the bimolecular photoreactions, one-electron reduction, and intramolecular isomerization. Cu(II) complexes of glyco-imino-aromatic conjugates in DNA binding, plasmid cleavage and cell cytotoxicity OH Amit Kumar, Atanu Mitra, Amrendra Kumar Ajay, Manoj Kumar Bhat HO O O O OH and Chebrolu P Rao . 1217–1228 Cu Cu N N HO O O Spectral studies primarily suggest that the complexes of C2-glucosyl conjugates O OH HO bind to DNA through intercalation. Copper complexes were found to cleave the plasmid DNA as well showed toxicity to HeLa and MCF–7 cell lines, suggestive of apoptotic cell death. Dinuclear complexes do bind better than the mononuclear ones. Cu(I)/Cu(II) templated functional pseudorotaxanes and rotaxanes Subrata Saha and Pradyut Ghosh . 1229–1237 The synthetic strategies developed to construct pseudorotaxanes and rotaxanes using Cu(I)/Cu(II) ions as template and interesting properties of selected threaded complexes are discussed. Linear, branched and network polysilanes with thienyl/furyl substituted sila-alkyl side chains and their applications for the R synthesis of fluorescent silver nanoparticles/clusters Me Si Ravi Shankar, Usharani Sahoo, Vandana Shahi PhMeSiCl + ThMe Si(CH ) SiCl Na, THF 2 2 2 2 3 Si Si – RT x 1-x n and Manchal Chaudhary . 1239 1244 Ph R R= ThMe2Si(CH2)2 Synthetic methods for a few linear, branched and network polysilanes Branched polysilane bearing thienyl/furyl substituted sila–alkyl side chains are described. These polymers are useful precursors for in situ reduction of Ag(I) ions and afford stable polymer–silver nanoassemblies with control over the size domains. Photoluminescence properties of these nanoassemblies are also reported. Contents 1139 Chalcogenated Schiff bases: Complexation with palladium(II) and Suzuki coupling reactions Pradhumn Singh, G K Rao, Mohd Salman Karim and Ajai K Singh . 1245–1253 Chalcogenated Schiff bases of 5–chloroisatin (L1–L3), 2–(methythio)- benzaldehyde (L4), 2–acetylpyridine (L5) and benzaldehyde (L6–L7) and palladium complexes of L4–L7 have been synthesized and characterized by 1H, 13C{1H}, 77Se{1H} and 125Te{1H} NMR. The Pd–complexes of L6–L7 even at 0.006 mol% give good conversions in Suzuki−Miyaura coupling (TON upto 1.58 × 104). Click-generated triazole based ferrocene-carbohydrate bioconjugates: A highly selective multisignalling probe for Cu(II) ions Arunabha Thakur, Sinjinee Sardar 1.5x10-5 Electrochemical Spectrochemical – 4.0 and Sundargopal Ghosh . 1255 1260 1.0x10-5 3.5 3.0 5.0x10-6 2+ 2.5 The Cu -specific colorimetric sensors 2,C46H56O20N6Fe and 3, 0.0 2.0 Abs. Current (A) 1.5 -6 C H O N Fe based on ferrocene-carbohydrate bioconjugates, were -5.0x10 28 33 10 3 1.0 0.5 -1.0x10-5 designed and synthesized in good yields. Both the compounds 2 and 3 0.0 2+ 0.0 0.2 0.4 0.6 0.8 1.0 200300400500600700800 Potential (V) behave as selective chromogenic and electrochemical chemosensor for Cu ion Wavelength(nm) in aqueous environment. Metal derivatives of heterocyclic-2-thiones: Variable donor ability, C–S rupture and new structural motifs dmso Tarlok S Lobana and Razia Sultana . 1261–1268 CuBr + MeN NH air S The chemical reactivity of heterocyclic-2-thiones, namely, pyridine-2-thione (SNC5H5), imidazolidine-2-thione (SN2C3H6), imidazoline-2-thione (SN2C3H4), 1-methyl-imidazoline-2-thione (SN2C4H6) and thiazolidine-2- thione (S2NC3H5) towards different metal ions is described with special reference to the effect of solvents on synthesis, structures and rupture of C–S bond or C–N bond formation. Mechanistic studies of copper(II)-mediated oxidation of vic- dioxime to furoxan Oindrila Das and Tapan Kanti Paine . 1269–1273 Copper(II) salts in acetonitrile oxidize vic-dioximes to furoxans gave high yields under ambient conditions. A dioximate-copper(II)-dinitrosoalkene intermediate is implicated in the reaction pathway. Crystallization of organically templated phosphomolybdate cluster-based solids from aqueous solution Minakshi Asnani, Dinesh Kumar, T Duraisamy and Arunachalam Ramanan . 1275–1286 Two types of phosphomolybdate clusters, fully oxidised Strandberg-type, VI V {P2Mo5 O23} and fully reduced {P4Mo6 O31} are crystallized with appropriate inorganic and/or organic cations from aqueous solutions containing sodium molybdate and an organic amine (morpholine, HMTA and ethylenediamine). The paper discusses the influence of pH and temperature in dictating the nature of the cluster and the supramolecular interactions. 1140 Contents Calixarenes: Versatile molecules as molecular sensors for ion )) recognition study α 2 1.2x107 0 Subrata Patra, Debdeep Maity, Ravi Gunupuru, Pragati Agnihotri 8.0x106 (Log(Fo-F)/(F-F – O OH OH O -6.3 -5.6 -4.9 and Parimal Paul . 1287 1299 Log[M] O O 4.0x106 NH HN Ion-recognition property of a large variety of calix[4]arenes incorporating Hg2+ crown moiety to make hybrid ionophore, substituents to impose steric crowding 0.0 N N 336 392 448 and fluoregenic moieties as signalling unit has been reported. This report demonstrates how factors such as sizes of the ionophore and metal ions, donor atoms, steric crowding and solvents, influence ion-selectivity. Synthesis, characterization and phosphotriesterase mimetic activity of some Zn(II) and Cu(II) complexes Mamata Singh, Ray J Butcher, Jerry P Jasinski, James A Golen and Govindasamy Mugesh . 1301–1313 Synthesis and phosphotriesterase (PTE) activity of three Zn(II) and Cu(II) complexes based on bis-phenolate ligands are described. The structures of these complexes were studied by spectroscopic and single crystal X-ray techniques. The mononuclear Zn(II) complex having coordinated water ligands exhibited high PTE activity as compared to the binuclear Zn(II) and Cu(II) complexes. Fabrication of optochemical and electrochemical sensors using thin films of porphyrin and phthalocyanine derivatives Palanisamy Kalimuthu, Arumugam Sivanesan – 20 and S Abraham John . 1315 1325 10 Thin films of meso-tetramesitylporphyrin on glass slide and 1,8,15,22- tetraaminometallophthalocyanine on GC electrode were fabricated for the 0 –0.2 0 0.2 0.4 0.6 optochemical detection of HCl gas and electrochemical determination of L-cysteine. E/V vs. Ag/AgCl (KCl sat) Photocytotoxic lanthanide complexes Akhtar Hussain and Akhil R Chakravarty . 1327–1342 The emerging chemistry of lanthanide complexes showing photo-induced DNA cleavage activity and photocytoxicity in cancer cells is reviewed. Lanthanide complexes of pyridyl bases show significant photocytotoxicity in HeLa cells in UV-A light of 365 nm. The cell death