Organotin-oxo clusters

This thesis reports on the development and expansion of reliable synthetic di-and multi-tin precursors for the assembly of oligomeric organotin-oxo compounds in which the shape, dimension and tin nuclearity can be controlled. The reaction of polymeric diorganotin oxides, (R2SnO)m (R = Me, Et, n-Bu, n-Oct, c-Hex, i-Pr, Ph), with saturated aqueous NH4X solutions (X = F, Cl, Br, I, OAc) in refluxing 1,4-dioxane afforded in high yields dimeric tetraorganodistannoxanes, [R2(X)SnOSn(X)R2]2, and in a few cases diorganotin dihalides or diacetates, R2SnX2. This method appears to be particularly good for the synthesis of halogenated tetraorganodistannoxanes but a less suitable method for the preparation of dicarboxylato tetraorganodistannoxanes. Identification of [R2(OH)SnOSn(X)R2]2 (R = n-Bu; X = Cl, Br) and [R2(OH)SnOSn(X)R2][R2(X)SnOSn(X)R2] suggest a serial substitution mechanism starting from [R2(OH)SnOSn(OH)R2]2. A series of α, ω -bis(triphenylstannyl)alkanes, [Ph3Sn]2(CH2)n (n = 3-8, 10, 12) and some of their derivatives were synthesised and characterised. These α, ω-bis(triphenylstannyl)alkanes, [Ph3Sn]2(CH2)n were converted to the corresponding halides [R(Cl)2Sn]2(CH2)n (R = CH2SiMe3) and subsequently to the polymeric oxides {[R(0)Sn]2(CH2)n}m. Reaction of {[R(O)Sn]2(CH2)n}m with [R(Cl)2Sn]2(CH2)n. (n = 3, n' = 4 and n = 4, n' = 3) in toluene at 100°C results in a mixture of symmetric and asymmetric double ladders, where different spacer chain lengths (n and n') provide the source of asymmetry. The coexistence at high temperature of separate 119Sn NMR signals belonging to symmetric and asymmetric double ladders suggests an equilibrium that is slow on the 119Sn NMR time scale and the position of which is temperature dependent. However, 119Sn NMR spectroscopic experiments of {[R(0)Sn]2(CH2)3}m with [R(Cl)2Sn]2(CH2)n for longer spacers (n - 5, 6, 8, 10, 12) reveal that molecular self-assembly of symmetric spacer-bridged di-tin precursors of equal chain length is preferred over asymmetric species. An ether-bridged di-tin tetrachloride [R(Cl)2Sn(CH2)3]2O (R = CH2SiMe3) and its corresponding polymeric oxide {[R(O)Sn(CH2)3]2O}m were synthesised and characterised. Reaction of [R(Cl)2Sn(CH2)3]2O with {[R(O)Sn(CH2)3]2O}m results in a unique functionalised double ladder {{[RSn(Cl)](CH2)3O(CH2)3[RSn(Cl)]}O}4 whose structure in the solid state was determined by X-ray analysis. Identification of tetrameric functionalised double ladder as well as dimeric and monomeric species suggest the existence of an equilibrium in solution. The feasibility of the functionalised double ladder to form host-guest complexes with a variety of metal cations is investigated using electrospray mass spectrometry (ESMS). Evidence for such complexes is found only for sodium cations. The reaction between {[R(O)Sn]2(CH2)n}m (n = 3, 4, 8, 10) and triflic acid is described. The initial formed products [RSn(CH2)nSnR](OTf)4 are easily hydrolysed. For n = 3, self-assembly leads to a discrete double ladder type structure, {{[RSn(OH)](CH2)3[RSn(H2O)]}O}44OTf, which is the first example of a cationic double ladder. For n ≥ 3, hydrolysis gives polymeric products, as demonstrated by the crystal structure of {[(H2O)(OH)RSn]2(CH2)4-2OTf2H2O}m. Two spacer-bridged terra-tin octachlorides [R(Cl)2Sn(CH2)3Sn(Cl)2]2(CH2)n (R = CH2SiMes; n = 1, 8) and their corresponding polymeric oxides {[R(O)Sn(CH2)3Sn(O)]2(CH2)n}m were successfully synthesised and characterised. Attempts were made to synthesise quadruple ladders from these precursors. Reactions of [R(Cl)2Sn(CH2)3Sn(Cl)2]2CH2 with {[R(O)Sn(CH2)3Sn(O)]2CH2}m or (Y-Bu2SnO)3 result in, mostly insoluble, amorphous solids. Reactions of [R(Cl)2Sn(CH2)3Sn(Cl)2]2(CH2)8 with {[R(O)Sn(CH2)3Sn(O)]2(CH2)8}m or (t-Bu2SnO)s result in new tin-containing species which are presumably oligomeric. The synthesis of a series of alkyl-bridged di-tin hexacarboxylates [(RCO2)3Sn]2(CH2)n (n = 3, 4; R = Ph, c-C6H11, CH3, C1CH2) is also reported. The hydrolysis of these compounds is facile and complex. There appears to be no correlation between spacer chain length and hydrolysis product. However, the conjugate acid strength of the carboxylate does appear to be important. In general only insoluble amorphous polymeric organotin-oxo compounds were obtained.

Automatic parallelisation and execution of applications on clusters

Parallel execution is a very efficient means of processing vast amounts of data in a small amount of time. Creating parallel applications has never been easy, and requires much knowledge of the task and the execution environment used to execute parallel processes. The process of creating parallel applications can be made easier through using a compiler that automatically parallelises a supplied application. Executing the parallel application is also simplified when a well designed execution environment is used. Such an execution environment provides very powerful operations to the programmer transparently. Combining both a parallelising compiler and execution environment and providing a fully automated parallelisation and execution tool is the aim of this research. The advantage of using such a fully automated tool is that the user does not need to provide any additional input to gain the benefits of parallel execution. This report shows the tool and how it transparently supports the programmer creating parallel applications and supports their execution.

Diorganotin dications stabilized by neutral ligands in the solid state: [R2Sn(H2O)2(OPPh3)2](O3SCF3)2 (R = Me, Bu)

The synthesis of [R₂Sn(H₂O)₂(OPPh₃)₂](O₃SCF₃)₂ (R = Me (1), Bu (2)) by the consecutive reaction of R₂SnO (R = Me, Bu) with triflic acid and Ph₃PO is described. Compounds 1 and 2 feature dialkyltin(IV) dications [R₂Sn(H₂O)₂(OPPh₃)₂]^₂+ apparently stabilized by the neutral ligands in the solid state. Compounds 1 and 2 readily dehydrate upon heating at 105 and 86 °C, respectively. The preparative dehydration of 1 afforded [Me₂Sn(OPPh₃)₂(O₃SCF₃)](O₃SCF₃) (1a), which features both bidentate and non-coordinating triflate anions. In compounds 1 and 2 the ligands Ph₃PO and H₂O are kinetically labile in solution and undergo reversible ligand exchange reactions. Compounds 1, 1a and 2 were characterized by multinuclear solution and solid-state NMR spectroscopy, IR spectroscopy, electrospray mass spectrometry, conductivity measurements, thermogravimetry and X-ray crystallography.

Preemptive job scheduling policy for distributively-owned workstation clusters

Cluster computing has come to prominence as a cost-effective parallel processing tool for solving many complex computational problems. In this paper, we propose a new timesharing opportunistic scheduling policy to support remote batch job executions over networked clusters to be used in conjunction with the Condor Up-Down scheduling algorithm. We show that timesharing approaches can be used in an opportunistic setting to improve both mean job slowdowns and mean response times with little or no throughput reduction. We also show that the proposed algorithm achieves significant improvement in job response time and slowdown as compared to exiting approaches and some recently proposed new approaches.

A comparative study at the logical level of centralised and distributed recovery in clusters

Cluster systems are becoming more prevalent in today’s computer society and users are beginning to request that these systems be reliable. Currently, most clusters have been designed to provide high performance at the cost of providing little to no reliability. To combat this, this report looks at how a recovery facility, based on either a centralised or distributed approach could be implemented into a cluster that is supported by a check pointing facility. This recovery facility can then recover failed user processes by using checkpoints of the processes that have been taken during failure free execution.

Execution environments and benchmarks for the study of applications' scheduling on clusters

In this paper, we have demonstrated how the existing programming environments, tools and middleware could be used for the study of execution performance of parallel and sequential applications on a non-dedicated cluster. A set of parallel and sequential benchmark applications selected for and used in the experiments were characterized, and experiment requirements shown. 

Building autonomic clusters : a response to IBM’s autonomic computing challenge

IBM has announced Autonomic Computing as one of its Grand Challenges. A list of characteristics was generated to describe an autonomic computing system. Many researchers and research group have responded positively to the challenge by initiating research around one or two of the characteristics identified by IBM as the requirements for Autonomic Computing. We have addressed the IBMrsquos request to contribute to the challenge by building an autonomic operating system that possesses nearly all IBM characteristics. This paper contains our response to the IBMrsquos Autonomic Computing Challenge.

Toward an operating system that supports parallel processing on nondedicated clusters

Present operating systems are not built to support parallel computing on clusters - they do not provide services to manage parallelism, i.e., to manage parallel processes and cluster resources. They do not provide support for both programming paradigms, Message Passing (MP) or Distributed Shared Memory (DSM). Due to poor operating systems, users must deal with computers of a cluster rather than to see this cluster as a single powerful computer. There is a need for cluster operating systems. We claim that it is possible to develop a cluster operating system that is able to efficiently manage parallelism, support MP and DSM and offer transparency. To substantiate this claim the first version of a cluster operating system managing parallelism and offering transparency, called GENESIS, has been developed.

Toward highly available, self-healing, adaptable, grid-like and user friendly nondedicated clusters

The human body was used to illustrate an Autonomic Computing system that possesses self-knowledge, self-configuration, self-optimization, self-healing, and self-protection, knowledge of its environment and user friendliness properties. Autonomic Computing was identified by IBM as one of the Grand Challenges. Many researchers and research groups have responded positively to the challenge by initiating research around one or two of the characteristics
identified by IBM as the requirements for Autonomic Computing. One of the areas that could benefit from the comprehensive approach created by the Autonomic Computing vision is parallel processing on nondedicated clusters. This paper shows a general design of services and initial implementation of a system that moves parallel processing on clusters to the computing mainstream using the Autonomic Computing vision.

Building autonomic clusters: a response to IBM's autonomic computing challenge

IBM has announced Autonomic Computing as one of its Grand Challenges. A list of characteristics was generated to describe an autonomic computing system. Many researchers and research group have responded positively to the challenge by initiating research around one or two of the characteristics identified by IBM as the requirements for Autonomic Computing. We have addressed the IBMs request to contribute to the challenge by building an autonomic operating system that possesses nearly all IBM characteristics. This paper contains our response to the IBMs Autonomic Computing Challenge.

Knowledge management for SME-based regional clusters

This paper considers the need for knowledge management (KM) in regional clusters comprising many small and medium enterprises (SMEs) and the appropriate KM techniques for this form of economic organisation. Information and communication technologies offer a range of tools to help such clusters develop into electronically-linked eClusters, making KM possible on a scale not previously possible. Most KM techniques have been developed by large organisations and their relevance to SME-based clusters has received little attention. Based on our analysis of the literature, we conclude that KM approaches based on personalised rather than codified information are the most promising model for regionally-based eClusters and that Communities of Practice arising from open forms of internet collaboration are most likely to be successful in this environment. Future research will identify key issues and appropriate techniques for supporting regional clusters with electronic systems for KM.