Home About us Contact
|
Home About us Contact | ||
|
|
||
Coordination
Kinds of Coordination Terms modified by Coordination Selected AbstractsPARENTING COORDINATION: IMPLEMENTATION ISSUES1FAMILY COURT REVIEW, Issue 4 20032003 AFCC Task Force on Parenting Coordination, April 30 ABSTRACT The parenting coordinator model ("PC model") has been implemented in many states as an intervention for dealing with high conflict families in domestic relations proceedings before the courts. The PC model has been repeatedly recommended by professionals as an intervention to help families structure, implement, and monitor viable parenting plans and to reduce relitigation rates where high conflict threatens the family adjustment process. This article summarizes current professional literature on the PC model and discusses the PC model as it has been implemented in various states, outlining the implementation issues encountered. This information may serve as a guide for determining the feasibility of establishing the PC model in other jurisdictions, and provides insight into potential impediments and possible resolutions. [source] COORDINATION OF MONETARY AND FISCAL POLICY IN A MONETARY UNION: POLICY ISSUES AND ANALYTICAL MODELSTHE MANCHESTER SCHOOL, Issue 2007Article first published online: 9 AUG 200, MATTHEW B. CANZONERI The European Monetary Union raises new and interesting questions about the coordination of monetary and fiscal policy. In this lecture, I discuss some of these questions and the answers that a new class of models,new neoclassical synthesis (NNS) models,is currently giving to them. I will argue that the new questions expose some weaknesses in current NNS modeling; in particular, the models do not seem to explain the positive correlation between national inflation and growth differentials that has been observed in the European data. I also review some recent work that has been done on policy coordination within a currency union. [source] Multi-Agent Distributed Coordination of Project Schedule ChangesCOMPUTER-AIDED CIVIL AND INFRASTRUCTURE ENGINEERING, Issue 6 2003Keesoo Kim This article presents the design and implementation of a multi-agent system called Distributed Subcontractor Agent System (DSAS), which consists of multiple subcontractor agents, multiple Graphic User Interfaces (GUIs), and an Agent Message Router. In the DSAS, subcontractors interact with their software agents to evaluate the impact of changes, simulate decisions, and get the negotiation results that they need to reschedule the project. This also presents the design and results of DSAS charrette tests, which demonstrated that DSAS produces the lower-cost results faster than manual centralized processes. DSAS can be useful for other domains, such as Mechanical, Electrical, and Plumbing (MEP) coordination and workspace management, if the appropriate agents are designed. [source] On coordination and its significance to distributed and multi-agent systemsCONCURRENCY AND COMPUTATION: PRACTICE & EXPERIENCE, Issue 4 2006Sascha Ossowski Abstract Coordination is one of those words: it appears in most science and social fields, in politics, warfare, and it is even the subject of sports talks. While the usage of the word may convey different ideas to different people, the definition of coordination in all fields is quite similar,it relates to the control, planning, and execution of activities that are performed by distributed (perhaps independent) actors. Computer scientists involved in the field of distributed systems and agents focus on the distribution aspect of this concept. They see coordination as a separate field from all the others,a field that rather complements standard fields such as the ones mentioned above. This paper focuses on explaining the term coordination in relation to distributed and multi-agent systems. Several approaches to coordination are described and put in perspective. The paper finishes with a look at what we are calling emergent coordination and its potential for efficiently handling coordination in open environments. Copyright © 2005 John Wiley & Sons, Ltd. [source] Coordinating components in middleware systemsCONCURRENCY AND COMPUTATION: PRACTICE & EXPERIENCE, Issue 13 2003Matthias Radestock Abstract Configuration and coordination are central issues in the design and implementation of middleware systems and are one of the reasons why building such systems is more complex than constructing stand-alone sequential programs. Through configuration, the structure of the system is established,which elements it contains, where they are located and how they are interconnected. Coordination is concerned with the interaction of the various components,when an interaction takes place, which parties are involved, what protocols are followed. Its purpose is to coordinate the behaviour of the various components to meet the overall system specification. The open and adaptive nature of middleware systems makes the task of configuration and coordination particularly challenging. We propose a model that can operate in such an environment and enables the dynamic integration and coordination of components by observing and coercing their behaviour through the interception of the messages exchanged between them. Copyright © 2003 John Wiley & Sons, Ltd. [source] Channel Coordination for a Supply Chain with a Risk-Neutral Manufacturer and a Loss-Averse Retailer,DECISION SCIENCES, Issue 3 2007Charles X. Wang ABSTRACT This articles considers a decentralized supply chain in which a single manufacturer is selling a perishable product to a single retailer facing uncertain demand. It differs from traditional supply chain contract models in two ways. First, while traditional supply chain models are based on risk neutrality, this article takes the viewpoint of behavioral principal,agency theory and assumes the manufacturer is risk neutral and the retailer is loss averse. Second, while gain/loss (GL) sharing is common in practice, there is a lack of analysis of GL-sharing contracts in the supply chain contract literature. This article investigates the role of a GL-sharing provision for mitigating the loss-aversion effect, which drives down the retailer order quantity and total supply chain profit. We analyze contracts that include GL-sharing-and-buyback (GLB) credit provisions as well as the special cases of GL contracts and buyback contracts. Our analytical and numerical results lend insight into how a manufacturer can design a contract to improve total supply chain, manufacturer, and retailer performance. In particular, we show that there exists a special class of distribution-free GLB contracts that can coordinate the supply chain and arbitrarily allocate the expected supply chain profit between the manufacturer and retailer; in contrast with other contracts, the parameter values for contracts in this class do not depend on the probability distribution of market demand. This feature is meaningful in practice because (i) the probability distribution of demand faced by a retailer is typically unknown by the manufacturer and (ii) a manufacturer can offer the same contract to multiple noncompeting retailers that differ by demand distribution and still coordinate the supply chains. [source] Flow Coordination and Information Sharing in Supply Chains: Review, Implications, and Directions for Future ResearchDECISION SCIENCES, Issue 4 2002Funda Sahin ABSTRACT Advances in information technology, particularly in the e-business arena, are enabling firms to rethink their supply chain strategies and explore new avenues for inter-organizational cooperation. However, an incomplete understanding of the value of information sharing and physical flow coordination hinder these efforts. This research attempts to help fill these gaps by surveying prior research in the area, categorized in terms of information sharing and flow coordination. We conclude by highlighting gaps in the current body of knowledge and identifying promising areas for future research. [source] Coordination of development and metabolism in the pre-midblastula transition zebrafish embryoDEVELOPMENTAL DYNAMICS, Issue 7 2008Bryce A. Mendelsohn Abstract To define the mechanisms that coordinate early embryonic development and metabolism, we have examined the response of zebrafish embryos to anoxia before the midblastula transition. Our findings reveal that anoxic pre-midblastula transition embryos slow the cell cycle, arrest before the midblastula transition and can recover normally if restored to a normoxic environment. Analyses of respiratory rates reveal that pre-midblastula transition embryos are less reliant on oxidative phosphorylation than older embryos. Interestingly, arrest in anoxia occurs despite inhibition of zygotic transcription, revealing a central role for maternal factors in the response to energy limitation. Consistent with this concept, we demonstrate that the posttranslational energy-sensing AMP-activated protein kinase pathway is activated in anoxia in pre-midblastula transition embryos. Taken together, these findings demonstrate a maternal program capable of coordinating developmental rate and metabolism in the absence of transcription-based pathways or cell cycle checkpoints. Developmental Dynamics 237:1789,1798, 2008. © 2008 Wiley-Liss, Inc. [source] Peer Commmentaries on Jonas Langer's The descent of cognitive developmentDEVELOPMENTAL SCIENCE, Issue 4 2000Article first published online: 28 JUN 200 Robert W. Mitchell, The role of perception in cognitive development, p. 379 Sue T. Parker, Cascading possibilities through the ontogenetic window of opportunity, p. 381 Jacques Vauclair and Olivier Houde´, Coordination of actions, visual perception and inhibition in non-human and human primate development, p. 382 [source] Entrepreneurship, Money and Coordination: Hayek's Theory of Cultural Evolution.ECONOMICA, Issue 301 2009By JURGEN G. BACKHAUS No abstract is available for this article. [source] Fiscal Policy Coordination and International TradeECONOMICA, Issue 294 2007TORBEN M. ANDERSEN While assertions are often made that non-cooperative fiscal policies suffer a contractionary bias, general equilibrium models have shown that the bias is unambiguously expansionary. This paper argues that the latter result relies on a particular and critical way of modelling international trade, and that under a more plausible trade structure, it is possible that fiscal policy is insufficiently expansionary in the non-cooperative case. Non-cooperative policy-making thus implies that fiscal policies are used too little if they expand private employment, and too much if they contract private employment. Inefficiencies in non-cooperative fiscal policies worsen when product markets become more integrated. [source] Coordination and Motivation in Flat Hierarchies: The Impact of the Adjudication CultureECONOMICA, Issue 288 2005Rabindra Nath Chakraborty This paper considers a variation of the partnership game with imperfect public information, in which teams are semi-autonomous. The only hierarchical intervention in teamwork is when a superior is called in by a team member to adjudicate alleged cases of free-riding or unjustified lateral punishment (flat hierarchy) according to publicly known adjudicative rules (adjudication culture), using for statistical inference a publicly known organizational norm for teamwork cooperation. It is shown that it is advantageous to set a non-elitist organizational teamwork norm. Furthermore, fairness in adjudication is valuable for economic reasons alone. [source] Vocal Coordination of Group Movement by Green Woodhoopoes (Phoeniculus purpureus)ETHOLOGY, Issue 1 2004A. N. Radford Communication signals are used by many species to maintain group cohesion when moving over larger areas. Groups of green woodhoopoes (Phoeniculus purpureus) generally move around their territory as a close-knit unit. Dominant individuals were more likely than subordinates to initiate movement to a new foraging site, but there was no intersexual difference. Dominants were also more likely than subordinates to be followed immediately. Vocalizations were shown to play an important role in mobilization: in the thick forests inhabited by woodhoopoes, visual cues to coordinate movement are likely to be less successful. When responding to the rallying call of a neighboring group, dominants and subordinates were equally likely to lead, as were males and females. As other group members followed immediately on most of these occasions, vocalizations were less important in this context than when moving to a new foraging site. [source] Synthesis and Photophysical Properties of LnIII,DOTA,Bipy Complexes and LnIII,DOTA,Bipy,RuII Coordination ConjugatesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 28 2010Miguel Vázquez López Abstract The synthesis and the systematic and comparative photophysical study of a series of visible (EuIII, TbIII) and NIR-emitting (NdIII, YbIII) lanthanide complexes (Ln2L) and ruthenium,lanthanide coordination conjugates (Ln2LRu) are reported. The GdIII complex, the GdIII,RuII coordination conjugate, as well as the RuII complex of the ligand H6L have also been synthesized and photophysically studied as control systems. The ligand H6L, composed of a central bipyridine binding unit and functionalized on each 5,-position with a DOTA macrocycle, has been successfully synthesized from cyclen, 5,5,-dimethyl-2,2,-bipyridine and 1,2-ethylendiamine in a nine-step process. Detailed luminescence studies of all complexes, including the determination of the quantum yield and lifetime, were carried out on finely powdered microcrystalline samples as well as in water, deuterated water and [D6]DMSO at ambient (295 K) and low temperature (77 K). The photophysical data corroborate the existence of energy transfer in the Ln2L complexes and in the Nd2LRu coordination conjugate. However, no (or at most, very little) energy transfer is takes place from the Ru(bipy)3 chromophore to the LnIII ion in the other Ln2LRu heteropolymetallic complexes. Moreover, the photophysical studies reveal that all the complexes and coordination conjugates adopt different conformations and hydration states in solution and in the solid state, which influences the efficiency of the energy transfer between the bipy and/or Ru(bipy)3 antennae and the LnIII ions. [source] New Approaches to 12-Coordination: Structural Consequences of Steric Stress, Lanthanoid Contraction and Hydrogen BondingEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 18 2010Anthony S. R. Chesman Abstract The anionic dinitrile ligand dicyanonitrosomethanide (dcnm), C(CN)2(NO),, and the anion resulting from its addition product with water, carbamoylcyanonitrosomethanide (ccnm), C(CN)(CONH2)(NO),, have been incorporated into lanthanoid complexes and display unusual ,2(N,O) nitroso coordination modes. (Et4N)3[Ln(ccnm)6] (1Ln; 1Ln = 1La, 1Ce, 1Pr, 1Nd, 1Sm) and (Me4N)3[Ln(ccnm)6] (2Ln; 2Ln = 2La, 2Ce, 2Pr, 2Nd) are systems containing 12-coordinate homoleptic trianionic lanthanoidate complexes. The nitroso groups of the ccnm ligands form three-membered ring chelates with the lanthanoid metal centre, with the asymmetry of the nitroso ,2 interactions dependent upon the intramolecular N,H···O=N hydrogen bonding. Additional intermolecular hydrogen bonding interactions exist between adjacent amide and nitrile groups giving rise to 3D ,-Po and 6,8-connected (412.63)(420.68) networks in 1Ln and 2Ln, respectively. The compounds (Me4N)3[Ln(dcnm)6] (3Ln; 3Ln = 3La, 3Ce, 3Nd, 3Sm) also contain a 12-coordinate trianionic lanthanoidate complex with the nitroso group exhibiting a highly symmetrical ,2 interaction. The sterically crowded environments of [Ln(18-crown-6)(dcnm)3] (4Ln; 4Ln = 4La, 4Ce, 4Pr, 4Nd) result in a shift towards a more asymmetric ,2 bonding of the nitroso group with decrease in the Ln3+ radius. There is a corresponding increase of the Ln,O,N angle, and one ligand is ,1(O) binding in 4Nd. The dcnm ligands in the discrete complexes [La(phen)3(dcnm)(3,x)Clx], x , 0.25 (5) (phen = 1,10-phenanthroline), (Et4N)[Ce(phen)2(dcnm)4] (6a/b, 6c) and [Ce(phen)2(dcnm)Cl2H2O] (7) display a variety of coordination modes. Complex 5 has 1D chains formed by ,,, stacking of adjacent phen co-ligands. Complexes 6 contain the monoanionic complex [Ce(phen)2(dcnm)4], with two geometric isomers present in the crystal structure of 6a/b. Complex 7 forms extended 1D chains via hydrogen bonding between coordinated water and chloride atoms and an extensive array of face-to-face , interactions. [source] Azido, Cyanato, and Thiocyanato Coordination Induced Distortions in Pentacoordinated [CoIIA(bip)]2 (A = NCS,, N3,, or NCO,) ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 31 2009Mrinal Sarkar Abstract A new family of distorted pentacoordinate [Co2] complexes was prepared and structurally characterized. In [CoIIA(bip)]2·S (1,3) [A = NCS,, N3,, NCO,; S = dmf, MeOH, dcm; Hbip = 2,6-bis(phenylmethyliminomethyl)-4-methylphenol], the nonbonded Co···Co separations are in the 3.243 to 3.254 Å range, and the pseudohalide-coordinated CoII ions are asymmetrically doubly bridged by the phenolate oxygen atoms of the ligand. The complementary basal,apical (b,a) and apical,basal (a,b) coordination modes of the phenolate bridges of bip, offer one O and two N donors for metal-ion coordination. In the three dinuclear complexes, the h.s. CoII ions are coupled antiferromagnetically to yield a singlet ground state. The solid-state variable-temperature magnetic susceptibility measurement data on the complexes were fitted to an isotropic Heisenberg dimer model that allowed estimation of the antiferromagnetic interactions for 1,3. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Oxido Pincer Ligands , Exploring the Coordination Chemistry of Bis(hydroxymethyl)pyridine Ligands for the Late Transition MetalsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2009Axel Klein Abstract Coordination of the 2,6-bis(hydroxymethyl)pyridine-based oxido pincer ligands RR,pydimH2 [R = R, = H (pydimH2); R = R, = Me (pydipH2); R = 2-tolyl, R, = Me (pydotH2)] towards late transition metals CoII, NiII, CuII, ZnII, PdII and PtII allows the formation of molecular species (complexes), which exhibit three main structural motifs in the solid state. The two main species are pentacoordinate [(RR,pydimH2)MCl2] and hexacoordinate [(RR,pydimH2)2M]X2, both of which are stable in solution and can be interconverted by changing the solvent polarity. The disproportionation equilibrium [(RR,pydimH2)MCl2] [rlhar2] [(RR,pydimH2)2M]2+ + [MCl4]2, was studied by optical spectroscopy. The chiral ligand pydotH2 allows the formation of chiral complexes. In the square-planar complexes [(pydimH2)2MCl2] (M = PdII or PtII) the oxido donor functions of the ligands do not take part in the coordination.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Highly Efficient Visible-Light-Induced Photocleavage of DNA by a Ruthenium-Substituted Fluorinated PorphyrinEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 11 2009Michelle Cunningham Abstract A new porphyrin, meso -5-(pentafluorophenyl)-10,15,20-tris(4-pyridyl)porphyrin, has been synthesized. Coordination of two [Ru(bipy)2Cl]+ moieties (where bipy = 2,2,-bipyridine) to the pyridyl nitrogen atoms in the 10,15-positions gives the target complex. Electronic transitions associated with the ruthenium,porphyrin include an intense Soret band and four less intense Q-bands in the visible region of the spectrum. An intense ,,,* transition in the UV region associated with the bipyridyl groups and a metal-to-ligand charge-transfer (MLCT) band appearing as a shoulder to the Soret band are also observed. Electrochemical properties associated with the complex include a redox couple in the cathodic region with E1/2 = ,0.84 V vs. Ag/AgCl attributed to the porphyrin and a redox couple in the anodic region at E1/2 = 0.79 V vs. Ag/AgCl due to the RuIII/II couple. DNA titrations and ethidium bromide displacement experiments indicate the ruthenium porphyrin interacts with DNA potentially through a partial intercalation mechanism. Irradiation of aqueous solutions of the ruthenated complex and supercoiled DNA at a 100:1 base pair/complex ratio with visible light above 400 nm indicates that the complex causes double-strand breaks of the DNA.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Pentadentate Ligands for the 1:1 Coordination of Lanthanide(III) SaltsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 3 2008Markus Albrecht No abstract is available for this article. [source] Pentadentate Ligands for the 1:1 Coordination of Lanthanide(III) Salts,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 20 2007Markus Albrecht Abstract Three hydrazone type ligands, namely 2 -H, 3, and 4, which were designed to form 1:1 complexes with lanthanoid(III) ions, are presented. Although the tetradentate ligand 2, leads to an interesting complex [(2)(2 -H)YCl2] with yttrium(III), a more general principle for the coordination of the metal ions by hydrazone-type ligands can be found with ligand 3, where 1:1 complexes are obtained with an effective coordination of the metal salts by the ligand. The stabledimer [{(3)Nd(CF3SO3)}2(,-CF3SO3)3]CF3SO3 was characterized by X-ray structure determination. Depending on the size of the metal ion, additional co-ligands can also be bound to the metal centers. This is observed in the molecular structures of [(3)Pr(NO3)2(MeOH)2](NO3), [(3)NdCl2(MeOH)(EtOH)]Cl, [(3)ErCl2(MeOH)]Cl, and [(3)LuCl2]Cl. The solid-state molecular structures of 4 and 4·HCl show the helicating ability of this ligand upon metal coordination. The corresponding lanthanide complexes of 4 are characterized by standard techniques such as NMR and CD spectroscopy and mass spectrometry.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Synthesis, Coordination and Catalytic Utility of Novel Phosphanyl,ferrocenecarboxylic Ligands Combining Planar and Central ChiralityEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 16 2007Martin Lama Abstract The chiral ferrocene derivative (R,Rp)-2-[1-(diphenylphosphanyl)ethyl]ferrocenecarboxylic acid (1) is prepared together with selected derivatives resulting from modification at the phosphane moiety [P -oxide (5) and P -sulfide (4)] and the carboxyl group {amides bearing benzyl (6) and (R)- or (S)-1-phenylethyl substituents [(R)- 7 and (S)- 7] at the amide nitrogen atom}. Acid 1 and amide 6 are studied as ligands in rhodium and palladium complexes. Bridge cleavage of the dimer [{Rh(,-Cl)Cl(,5 -C5Me5)}2] with 1 gives [RhCl2(,5 -C5Me5)(1 -,P)] (9) containing P-monodentate 1, which undergoes smooth conversion to the (phosphanylalkyl)ferrocenecarboxylato complex [RhCl(,5 -C5Me5){Fe(,5 -C5H5)(,5 -C5H3 -1-CH(Me)PPh2 -2-COO-,2O,P}] (10) upon treatment with silica gel or alumina. Yet another O,P -chelate complex,[Rh{Fe(,5 -C5H5)(,5 -C5H3 -1-CH(Me)PPh2 -2-COO-,2O,P}(CO)(PCy3)] (11; Cy = cyclohexyl) is obtained directly by an acid-base reaction between the acetylacetonato complex [Rh(acac)(CO)(PCy3)] and 1. Amide 6 reacts with [{Pd(,-Cl)(,3 -C3H5)}2] to give the expected phosphane complex [PdCl(,3 -C3H5)(6 -,P)] (12), while the replacement of the cyclooctadiene (cod) ligand in [PdCl(Me)(cod)] affords the chelate complex [PdCl(Me)(6 -,2O,P)] (13). All compounds are characterised by spectroscopic methods and the solid-state structures of 5, 9, 11, 13, (R,Sp)-2-[1-(diphenylphosphoryl)ethyl]-1-[N -(R)-(1-phenylethyl)carbamoyl]ferrocene [(R)- 8; phosphane oxide from (R)- 7], and the synthetic precursors (R,Sp)-1-bromo-2-[1-(diphenylphosphanyl)ethyl]ferrocene (2) and (R,Sp)-1-bromo-2-[1-(diphenylthiophosphoryl)ethyl]ferrocene (3) determined by single-crystal X-ray diffraction. The catalytic properties of 1 and the amides are probed in enanatioselective rhodium-catalysed hydrogenation and palladium-catalysed asymmetric allylic alkylation. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Receptor versus Counterion: Capability of N,N, -Bis(2-aminobenzyl)-diazacrowns for Giving Endo- and/or Exocyclic Coordination of ZnIIEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2007Lea Vaiana Abstract The structure of ZnII complexes with receptors L1 and L2[L1 = N,N, -bis(2-aminobenzyl)-1,10-diaza-15-crown-5 and L2 = N,N, -bis(2-aminobenzyl)-4,13-diaza-18-crown-6] was studied both in the solid state and in acetonitrile solution. Both receptors form mononuclear ZnII complexes in this solvent, while no evidence for the formation of dinuclear complexes was obtained. This is in contrast with previous investigations that demonstrated the formation of dinuclear complexes of L2 with first-row transition metals such as NiII, CoII and CuII. Compounds of formula [Zn(L1)](ClO4)2 (1), [Zn(L1)](NO3)2·2CH3CN (2), [Zn(L2)](ClO4)2 (3) and [Zn(L2)(NO3)2] (4) were isolated and structurally characterised by X-ray diffraction analyses. L1 forms seven-coordinate ZnII complexes in the presence of both nitrate and perchlorate anions, as a consequence of the good fit between the macrocyclic cavity and the ionic radius of the metal ion. The ZnII ion is deeply buried into the receptor cavity and the anions are forced to remain out of the metal coordination sphere. The cation [Zn(L1)]2+ present in 1 and 2 is one of the very few examples of seven-coordinate Zn complexes. Receptor L2 provides a very rare example of a macrocyclic receptor allowing endocyclic and exocyclic coordination on the same guest cation, depending on the nature of the anion present. Thus, in 3 the ZnII ion is endocyclically coordinated, placed inside the crown hole coordinated to four donor atoms of the ligand in a distorted tetrahedral environment, whereas in 4, the presence of a strongly coordinating anion such as nitrate results in an exocyclic coordination of ZnII, which is directly bound only to the two primarily amine groups of L2 and two nitrate ligands. Spectrophotometric titrations of [Zn(L2)]2+ with tetrabutylammonium nitrate in acetonitrile solution demonstrate the stepwise formation of 1:1 and 1:2 adducts with this anion in acetonitrile solution. The [Zn(L1)]2+, [Zn(L2)]2+ and [Zn(L2)(NO3)2] systems were characterised by means of DFT calculations (B3LYP model). The calculated geometries show an excellent agreement with the experimental structures obtained from X-ray diffraction analyses. Calculated binding energies of the macrocyclic ligands to ZnII are also consistent with the experimental data.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] N -(Aryl)picolinamide Complexes of Ruthenium: Usual Coordination and Strategic CyclometalationEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2007Sumon Nag Abstract Reaction of five N -(4- R -phenyl)picolinamides (R = OCH3, CH3, H, Cl, and NO2) with [Ru(PPh3)2(CO)2Cl2] in refluxing 2-methoxyethanol in the presence of a base (NEt3) affords two geometrical isomers of a group of complexes (1-R and 2-R), each of which contains an amide ligand coordinated to the metal center as a monoanionic bidentate N,N donor along with two triphenylphosphanes, a carbonyl, and a hydride. Similar reaction of N -(naphthyl)picolinamide with [Ru(PPh3)2(CO)2Cl2] affords an organometallic complex, 3, in which the amide ligand is coordinated to the metal center, by C,H activation of the naphthyl ring at the 8-position, as a dianionic tridentate N,N,C donor along with two triphenylphosphanes and one carbonyl. Structures of the 1-OCH3, 2-CH3, and 3 complexes have been determined by X-ray crystallography. In all the complexes the two triphenylphosphanes are trans. In the 1-R complexes the hydride is trans to the pyridine nitrogen and in the 2-R complexes it is trans to the amide-nitrogen. All the complexes are diamagnetic, and show characteristic 1H NMR signals and intense MLCT transitions in the visible region. Cyclic voltammetry on all the complexes shows a RuII,RuIII oxidation within 0.71,0.93 V versus SCE. An oxidation and a reduction of the coordinated amide ligand are also observed within 1.29,1.69 V versus SCE and ,1.02 to ,1.21 V versus SCE respectively.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Control of Intramolecular Ether-Oxygen Coordination in the Crystal Structure of Copper(II) Complexes With Dipicolylamine-Based LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2007Yuji Mikata Abstract Thirteen crystal structures of copper(II) complexes with a series of dipicolylamine (DPA)-derived ligands, N -(2-methoxyethyl)- N,N -bis(2-pyridylmethyl)amine (L1), N -[2-(2-hydroxyethyloxy)ethyl]- N,N -bis(2-pyridylmethyl)amine (L2) and N -(3-methoxypropyl)- N,N -bis(2-pyridylmethyl)amine (L3), have been determined and the factors that control the coordination of the ether-oxygen atom of these ligands to the copper centre are discussed. Complexes that have +1 or +2 charges exhibit coordination of the ether-oxygen atom, whereas neutral complexes in which two anions are bound to the copper(II) centre tend to lose the oxygen coordination. Upon chelation of the oxygen atom, L3 forms a six-membered chelate ring with respect to the 3-aminopropyl ether moiety whereas L1 and L2 form a five-membered chelate. This difference, especially in the nitrate and bromide complexes, determines whether the ether-oxygen atom chelates to the metal centre to give a monocationic complex, or the second anion coordinates to the metal centre to form the ether-free, neutral complex. The terminal anchor hydroxy group of L2 facilitates the ether-oxygen coordination via a hydrogen bond interaction to the donor atom located trans to the aliphatic nitrogen atom in the basal plane. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Diastereopure Cationic NCN-Pincer Palladium Complexes with Square Planar ,4 - N,C,N,O CoordinationEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 22 2006Silvia Gosiewska Abstract Neutral NCN-pincer palladium bromide complex 2 containing the monoanionic, enantiopure pincer ligand 2,6-bis{[(S)-2-hydroxymethyl-1-pyrrolidinyl]methyl}phenyl bromide (1) with bis- ortho -(S)-prolinol substituents was synthesized and isolated as a mixture of three stereoisomers [(SN,SN,SC,SC), (RN,SN,SC,SC), and (RN,RN,SC,SC)] in a 1:1:1 ratio. Upon abstraction of the bromide ion from the unresolved mixture of 2, single diastereoisomers of the cationic complexes [3]BF4 and [3]PF6, respectively, were formed with a unique,4 - N,C,N,O coordination mode of ligand 1. X-ray crystal structure determination established the intramolecular,4 - N,C,N,O coordination of 1 to palladium where the typical mer -,3 - N,C,N pincer coordination is accompanied by coordination of one of the hydroxy groups of the (S)-prolinol moieties. The water molecule that was cocrystallized in the crystal structure of [3]PF6 does not coordinate to palladium, but instead is involved in a hydrogen bonding network. The catalytic potential of both cationic complexes, [3]BF4 and [3]PF6, was tested in an aldol reaction of aldehydes with methyl isocyanoacetate to yield the oxazoline products as racemic mixtures.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] A Terephthalato-Bridged NiII Complex Capped with a Nonchelating Ligand Displays a Three-Dimensional Supramolecular Network Constructed by Coordination and Multi-Intermolecular ForcesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 23 2005Chang Seop Hong Abstract A new tp-bridged complex [Ni(pyrazole)4(tp)]n (1; tp = terephthalate) coordinated with a nonchelating pyrazole ligand has been synthesized and characterized using X-ray structure determination and magnetic studies. The crystal structure reveals that the capping ligand functions as a source of hydrogen bonding and intermolecular contacts, such as ,,, and CH,, interactions, that result in a three-dimensional supramolecular assembly. Weak antiferromagnetic couplings are transmitted between NiII centers through the tp linkage. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] endo and exo Coordination of Indanol: Synthesis, Isolation and Structural Characterisation of [H3Ru3(endo -Indanol)(C6Me6)2(O)]+ and [H3Ru3(exo -Indanol)(C6Me6)2(O)]+ as Their Tetrafluoroborate SaltsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 19 2004Ludovic Vieille-Petit Abstract The reaction of 2,3,4,7-tetrahydro-1H -inden-2-ol with ruthenium chloride hydrate in refluxing ethanol yields the chloro-bridged dinuclear complex [RuCl2(indanol)]2 (1). The mononuclear complex [Ru(indanol)(H2O)3]2+ (2), formed in situ from 1 in aqueous solution, reacts with the dinuclear complex [H3Ru2(C6Me6)2]+ to give a trinuclear arene-ruthenium cluster as a mixture of two isomers, the cations [H3Ru3(endo -indanol)(C6Me6)2(O)]+ (3a) and [H3Ru3(exo -indanol)(C6Me6)2(O)]+ (3b), in a 1:1 ratio. The hydroxy function of the indanol ligand is oriented towards the ,3 -oxo cap of 3a, whereas the OH group is bent away from the metal skeleton of 3b. These two isomers, which can easily be separated by silica-gel chromatography, were isolated and characterised as their tetrafluoroborate salts. The single-crystal X-ray structure analysis of [3a][BF4] shows a strong intramolecular hydrogen bond between the ,3 -oxo ligand and the hydroxyl function, which even persists in acetone solution, as demonstrated by NMR spectroscopy. On the other hand, the hydroxy function of 3b was found to be free in the solid state as well as in solution, as shown by an X-ray crystal structure analysis and by NMR spectroscopy. The catalytic activities of the water-soluble trinuclear cations 3a and 3b for the hydrogenation of benzene to give cyclohexane under biphasic conditions are considerably different, the exo isomer 3b being more active than the endo isomer 3a. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Novel Bonding Modes between Tetrathiafulvalenes (TTFs) and Transition Metal Centers: ,-Bonding and Covalent TTFSiMe2,MLn Coordination to PlatinumEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 13 2004Mathuresh N. Jayaswal Abstract Two novel strategies for coordinating TTF to transition metal centers have been developed. The reaction of tetrathiafulvalene (TTF) or 3,4-dimethyltetrathiafulvalene (o -Me2TTF) with [Pt(,2 -C2H4)(PPh3)2] leads to the , complexes [Pt(,2 -TTF)(PPh3)2] (1) and [Pt(,2 - o -Me2TTF)(PPh3)2] (2), respectively. An X-ray crystallographic study performed on 2 confirmed, that TTFs act as a , acidic ligand. NMR studies revealed the existence, in solution, of an equilibrium between free and complexed TTF. Dilithiation of o -Me2TTF and subsequent silylation with ClSiMe2H afforded 3,4-dimethyl-3,,4,-(dimethylsilyl)tetrathiafulvalene (3), which has been structurally characterized. 3 reacts by oxidative addition across [Pt(,2 -C2H4)(PPh3)2] to give [Pt{,2 - o -(SiMe2)2TTFMe2}(PPh3)2] (4), in which the TTF ligand is covalently ligated to platinum via SiMe2 bridges. The redox properties of 3 and 4 have been investigated by cyclic voltammetry. Strong cathodic shifts of the two redox processes were observed for 4, implying the TTF core. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] New Pentadentate Carboxylate-Derivatized Sulfur Ligands Affording Water Soluble Iron Complexes with [Fe(NS4)] Cores that Bind Small Molecules (CO, NO, PMe3) as Co-LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 3 2004Dieter Sellmann Abstract In the search for polydentate sulfur ligands that are able to form water-soluble iron complexes which can bind nitrogenase relevant molecules, the new pentadentate ligands pyCO2MeS4,H2 [2,6-bis[2-mercapto-3-(methoxycarbonyl)phenylthio]dimethylpyridine] (1) and pyCO2HS4,H2 [2,6-bis(2-mercapto-3-carboxyphenylthio)dimethylpyridine] (2) having NS4 donor atom sets and terminal thiolate donors have been synthesized. The starting material was CO2MeS2,H2 (2,3-dimercapto benzoic acid methyl ester) which was alkylated with 2,6-bis[(tosyloxy)methyl]pyridine. The problem of specifically achieving regioselective mono-alkylation of this 1,2-benzene-dithiol derivative was solved by carrying out the alkylation of CO2MeS2,H2 at ,78 °C in the presence of stoichiometric amounts of a base. Saponification of 1 afforded the carboxylic acid derivative. Coordination of pyCO2MeS42, to FeII in the presence of co-ligands (L = CO, PMe3) yielded the complexes [Fe(L)(pyCO2MeS4)] where L = CO (5) or PMe3 (4). Upon treatment with NOBF4, complex 5 afforded [Fe(NO)(pyCO2MeS4)]BF4 (7) which could be subsequently converted to the isolable 19 valence electron species [Fe(NO)(pyCO2MeS4)] (8) upon reduction with N2H4. In the absence of potential co-ligands, coordination of pyCO2MeS42, to FeII afforded the dinuclear complex [Fe(pyCO2MeS4)]2 (6) whilst coordination to NiII gave [Ni(pyCO2MeS4)]x (3). Solubility of these complexes in water could be achieved by replacing the CO2Me groups with CO2H substituents. The ligand pyCO2HS42, afforded the iron complexes [Fe(L)(pyCO2HS4)] [L = CO (10) and PMe3 (12)] and [Fe(NO)(pyCO2HS4)]BF4 (11). Both 10 and 12 could be reversibly deprotonated to give the corresponding water-soluble salts (NMe4)2[Fe(L)(pyCO2S4)] with L = CO {(NMe4)2 [9]} and PMe3 {(NMe4)2 [13]}. The complexes were characterized by elemental analysis, spectroscopic methods and X-ray structural determinations. The molecular structure of [Fe(PMe3)(pyCO2HS4)] (12) was found to exhibit inter- and intramolecular O,H···O and O,H···S hydrogen bonds which serve as models for proton transfer steps from external sources to the active sites of metal sulfur enzymes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Glutamatergic input governs periodicity and synchronization of bursting activity in oxytocin neurons in hypothalamic organotypic culturesEUROPEAN JOURNAL OF NEUROSCIENCE, Issue 12 2003Jean-Marc Israel Abstract During suckling, oxytocin (OT) neurons display a bursting electrical activity, consisting of a brief burst of action potentials which is synchronized throughout the OT neuron population and which periodically occurs just before each milk ejection in the lactating rat. To investigate the basis of such synchronization, we performed simultaneous intracellular recordings from pairs of OT neurons identified retrospectively by intracellular fluorescent labelling and immunocytochemistry in organotypic slice cultures derived from postnatal rat hypothalamus. A spontaneous bursting activity was recorded in 65% of OT neurons; the remaining showed only a slow, irregular activity. Application of OT triggered bursts in nonbursting neurons and accelerated bursting activity in spontaneously bursting cells. These cultures included rare vasopressinergic neurons showing no bursting activity and no reaction to OT. Bursts occurred simultaneously in all pairs of bursting OT neurons but, as in vivo, there were differences in burst onset, amplitude and duration. Coordination of firing was not due to electrotonic coupling because depolarizing one neuron in a pair had no effect on the membrane potential of its partner and halothane and proprionate did not desynchronize activity. On the other hand, bursting activity was superimposed on volleys of excitatory postsynaptic potentials (EPSPs) which occurred simultaneously in pairs of neurons. EPSPs, and consequently action potentials, were reversibly blocked by the non-NMDA glutamatergic receptor antagonist CNQX. Taken together, these data, obtained from organotypic cultures, strongly suggest that a local hypothalamic network governs synchronization of bursting firing in OT neurons through synchronous afferent volleys of EPSPs originating from intrahypothalamic glutamatergic inputs. [source] | |||||||||||||||||||||||||||||||||||||||||||||||||