Dillip Kumar Chand

Ring-opening polymerization (ROP) of maleic anhydride (MA) or L-Lactide (L-LA) with tert-butyl glycidyl ether (tBGE) were carried out in the presence of Ti and Zr complexes of benzoxazole substituted 8-hydroxyquinoline ligands (1a-3a and 1b-3b), delivering nearly alternative P(tBGE-co-MA) and block-like P(tBGE)-b-PLLA co-polymers with high molecular weight (Mn) and narrow to broad molecular weight distributions (Mw/Mn). The molecular structures of the Ti and Zr complexes (1a and 3b) were confirmed by single-crystal X-ray diffraction analysis. The Zr complex 3b exhibited superior reactivity and produced copolymers within one hour at 80 °C in dry toluene (Mn,GPC = 14–40 Kg mol-1 and Mw/Mn = 1.19–1.55). In case of P(tBGE-co-MA) copolymer synthesis, the polymer arm with tBGE fraction was building faster (82–100 unit%) compared to MA (52–99 unit%). In contrast, incorporation of L-LA was higher (82–99 unit%) compared to tBGE insertion (20–60 unit%) in P(tBGE)-b-PLLA copolymer synthesis.

A series of designed binuclear palladium(II)-based self-assemblies, [Pd2(en)2(L)2](NO3)4, 1a; [Pd2(tmeda)2(L)2](NO3)4, 2a; [Pd2(bpy)2(L)2](NO3) 4, 3a; and [Pd2(phen)2(L)2](NO 3)4, 4a, are synthesized. These complexes are obtained in good to excellent yields by equimolar combination of the nonchelating bidentate ligand bis(4-pyridylmethyl)piperazine, L, with the corresponding cis-protected palladium(II) component, that is, Pd(N-N)(NO3)2, under suitable reaction conditions. The cis-protecting N-N units used are ethylenediamine (en), tetramethylethylenediamine (tmeda), 2,2′-bipyridyl (bpy), and 1,10-phenanthroline (phen). The complexes 1a-4a are well-characterized by 1H NMR, H-H COSY, and HSQC, and the molecular compositions have been established by ESI-MS. The molecular structures are confirmed for the complexes [Pd2(tmeda)2(L) 2](ClO4)4, 2b; [Pd2(bpy) 2(L)2](ClO4)4, 3b; and [Pd 2(phen)2(L)2](NO3)4, 4a, by the single-crystal X-ray diffraction technique. In the cases of the complexes 3b and 4a, the crystal packing diagrams display a unique one-dimensional predefined organization of molecules by intermolecular π-π interactions using the strategically located π-surfaces of the cis-protecting units. This organization resembles a set of toppled dominos. A given set exhibits further interactions with the neighboring sets in the packing pattern that are influenced by the nature of the N-N moiety, for example, bpy or phen. However, no such arrangement is observed in the case of the complex 2b due to the lack of a π-surface at the cis-protecting moiety. © 2013 American Chemical Society.

A series of Ti(iv), Zr(iv) and Hf(iv) complexes are synthesized by complexation of [NNO]-type tridentate Schiff base ligands {2-amino-3-((E)-(2-hydroxybenzylidene)amino)maleonitrile}, L1(H)2; {2-amino-3-((E)-(2-hydroxy-3,5-dimethylbenzyl-idene)amino)maleonitrile}, L2(H)2 and {2-amino-3-((E)-(3-(tert-butyl)-2-hydroxy-5-methylbenzylidene)amino)maleonitrile}, L3(H)2 with suitable group 4 metal alkoxides. The ligands are derived by the mono-condensation of diaminomaleonitrile and salicylaldehyde derivatives. All the complexes are found to be dinuclear on the basis of their NMR and MS spectral data. Three of the nine complexes are structurally characterized by single crystal X-ray diffraction studies. The crystal structures confirmed the dinuclear nature of these complexes. The metal centers of the dinuclear core are connected through two bridging alkoxy groups. The coordination environment of a metal center comprises one unit of a di-deprotonated ligand, one unit of a terminal alkoxide and two units of the bridging alkoxide groups, so as to form distorted octahedral complexes. The catalytic activities of these complexes were investigated towards the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) and rac-lactide (rac-LA) in bulk. These complexes were found to be highly active catalysts for the production of PCL [poly(caprolactone)] and PLA [poly(lactic acid)] with a high rate of conversion. The strong electron withdrawing cyano groups present in these complexes rationalized the high polymerization activity. The polymers exhibited narrow molecular weight distributions (MWDs). Furthermore, the isolated PLAs were remarkably heterotactic-rich with maximum Pr = 0.80, by using an Hf catalyst with tert-butyl substituent on the ortho-position of the phenolic moiety. These complexes are moderately active towards the ring-opening homopolymerization of rac-epoxides, such as rac-cyclohexene oxide (rac-CHO), rac-propylene oxide (rac-PO) and rac-styrene oxide (rac-SO). These complexes exhibited good activity in ethylene polymerization upon activation with co-catalyst MAO and with a bulky substituent on the ortho-position of the phenolic moiety of the catalysts.

A series of salicylbenzoxazole pro-ligand 2-(5-X-benzoxazol-2-yl)-6-R1-4-R2-phenol, L1H-L4H were subjected to reaction with titanium, zirconium and hafnium alkoxides. The substituents (R1, R2, X) present in the pro-ligand back bone are (H, H, H) for L1H; (H, H, Cl) for L2H; (Br, Br, H) for L3H; and (Cl, Cl, H) for L4H. The mononuclear Ti complexes, 1a-4a of [M(L)2(OiPr)2] formulation were prepared by combining the pro-ligands L1H-L4H with Ti(OiPr)4 in dry toluene. However, with the addition of H2O (0.5 M equiv.), the controlled hydrolysis of Ti complex 4a in a mixed solvent of THF/toluene produced oxo-bridged dinuclear Ti complex 5a having [M(μ-O)(L)2(OiPr)]2 formulation in good yield (≥75%) using L4H as the pro-ligand. The composition of the mononuclear Zr and Hf complexes of L1H-L4H are found to be quite similar to that of the Ti complexes. Additionally, mononuclear Zr complexes 1b-4b and Hf complexes 1c-4c were prepared. The oxo-bridged dinuclear Zr and Hf complexes 5b and 5c were isolated from the controlled hydrolysis reactions of mononuclear Zr and Hf complexes 4b and 4c. All these complexes were well characterized and crystal structure of six of the fifteen complexes were determined. These complexes were used as initiators for the ring-opening polymerization (ROP) of rac-LA, copolymerization of L-LA with ε-CL and homopolymerization of rac-epoxides. In particular, the dinuclear Zr complex (5b) was found to exhibit extremely high activity in these polymerization studies. Iso-enriched polymers were observed upon using the Zr and Hf complexes of the pro-ligands L3H or L4H as the initiator. DFT studies have been carried out on the ROP of lactides initiated by the Ti, Zr and Hf complexes 1a, 1b and 1c. The results indicated that the activation barrier to reach the transition state using Zr complexes is lower and hence facile as compared to the Ti and Hf complexes.

One-pot synthesis of self-assembled heteroleptic complexes of general formula [Pdx(tmeda)x(L)y](NO3) 2x is achieved by combining required amount of tmeda, a chosen ligand L and Pd(NO3)2 under suitable reaction conditions. The strategy is devised using our understanding of a special variety of ligand exchange reactions (LER) around palladium(II) centers as modeled in this work. The one-pot synthesis technique is thus considered as an application of the unique LER. © 2013 Elsevier B.V.

Six new cis-dioxomolybdenum(VI) complexes of chiral Schiff-base ligands, derived from condensation of various amino alcohols and substituted salicylaldehydes, have been prepared and characterized by NMR, IR, ESI-MS and single crystal X-ray diffraction techniques. The geometry around the molybdenum center is distorted octahedral in which a tridentate Schiff-base ligand with two anionic oxygens and one neutral imine nitrogen occupies meridional position. The octahedral geometry of the cis-dioxomolybdenum center is additionally completed by a coordinated labile solvent molecule. In some complexes the sixth site is found to be vacant where the relatively bulky substituents hinder the coordination of the solvent. These complexes are tested for catalytic enantioselective sulfoxidation reactions using hydrogen peroxide as oxidant at low temperature which shows high selectivity along with good to moderate enantiomeric excess. ESI-MS study of the reaction mixture indicates the formation of oxoperoxoMo(VI) complexes during catalysis. The steric effect originated from the substituent on chiral ligand on the catalytic reaction is also discussed. It is found that the substituents at the β position of the amino alcohol seem to greatly influence the enantioselectivity of the oxidation reactions. © 2011 Elsevier B.V. All rights reserved.

An intriguing phenomenon of a hitherto unknown type of cavity induced "reductive encapsulation" using Hg(ii) and a homoditopic octaaza cryptand is described. The crystal structure of the complex offers a new type of grid-like polydodecameric water-chloride cluster, {[(H2O) 12(Cl)]1-}n, that renders the highest number of water molecules per chloride reported thus far. This journal is © the Partner Organisations 2014.

In the solution state, an equimolar mixture of syn- and anti-conformations is present for the ligand N,N′-bis(4-pyridylformyl)piperazine, L. Combining L with cis-Pd(en)(NO3)2 resulted in the formation of metallomacrocycle cis-[Pd2(en)2(L) 2](NO3)4, 1, quantitatively. Coordinated L in complex 1 was found to exist exclusively in the syn-conformation. The equimolar mixture of syn- and anti-conformations was re-established by ethylenediamine induced demetallation of 1. © 2014 the Partner Organisations.

A surfactant based molybdenum system that exhibits catalytic activity for sulfoxidation reactions of various organic sulfides in aqueous medium has been developed and comprehensively characterized using IR, XRD, NMR, ESI-MS, DLS and TEM. The catalyst showcases remarkable selectivity for the preparation of both sulfoxides and sulfones in the range of good to excellent yields. Furthermore, the catalyst showed a high degree of tolerance towards various sensitive functional groups such as hydroxyl, acetal, aldehyde, amine, imine, oxime, cyano and alkene. © the Partner Organisations 2014.

A series of silver(i)-based coordination polymers (AgCPs) have been synthesized using three new nonchelating cis-bis-nitrile derivatives of oxa-bowls, L1-L3, as ligand components. The ligands are designed to provide conformational restrictions as well as semi-rigid directionality to the coordination vectors extended from the nitrile functionalities. The steric bulks around the oxa-bowl spacer moieties are gradually escalated to study their influence on the topologies of the ensuing AgCPs. Two silver salts i.e. AgSbF6 and AgPF6 are used to check the influence of anions on the structural architectures. Ziz-zag-sheet type 2-D AgCPs are formed with the ligands L1 and L2 possessing less steric bulk. All the metal centres are found to be tetracoordinated by nitrile-nitrogens of the same sheet giving distorted-bisphenoidal geometries. Additional short interactions of the silver(i) centres of a given sheet with the oxygen of the oxa-bowls belonging to the neighbouring stacked sheets are observed. The bulky ligand L3 behaved differently where the metal centres are tetracoordinated although only two of the ligating units are derived from the nitrile nitrogens and the remaining two are from, depending upon the counter anion, the counter anion/oxygen of oxa-bowls or two water molecules. The overall arrangements in the AgCPs of L3 are of the 2-D carpet type (for SbF6- ion) composed of interconnected chains, and 1-D ladder type (for PF6- ion) constructed from two chains. Cation-π interactions are found between the aromatic part of L3 of a given chain and the silver(i) of the adjacent chain that are interdigitated. © 2013 The Royal Society of Chemistry.