This thesis describes the synthesis and chemistry of triangular phosphido-bridged iridium clusters. The cluster [Ir3(μ-PPh2)3 (CO)6] was obtained analytically pure for the first time. In the solid state this 48 electron cluster exhibits one short iridium-iridium bond of 2.6702(3) Å and two long iridium-iridium bonds, 2.9913(3) Å on average. Two phosphido bridges rest closely within the plane of the metal triangle while the unique phosphido group, bridging the short metal-metal bond, is almost orthogonal to this plane. NMR data suggest that this structure is also adopted in solution below 183 K. At higher temperature however the phosphido bridges give rise to an average signal which is presumably due to a rapid flip-flop motion of these groups. Addition of one molar equivalent of dimethylacetylendicarboxylate to [Ir3(μ-PPh2)3(CO)6] results in formation of [Ir3(μ-PPh2)3(CO) 6(μ-DMAD)] which contains a diiridacyclobutene. Addition of excess alkyne leads to the CO-inserted [Ir3(μ-PPh2) 3(CO)5(μ-DMAD){κ2-MeO 2CCC(CO2Me)C(O)}] which photochemically decarbonylates, to give [Ir3(μ-PPh2)3(CO)5(μ-DMAD) 2]. The 50 electron cluster [Ir3(μ-PPh2) 3(CO)5(t-BuNC)2] also reacts with dimethylacetylendicarboxylate to yield the CO-inserted [Ir3(μ-PPh2)3(CO) 3(t-BuNC)2{κ2-MeO2CCC(CO 2Me)C(O)}2] in two isomeric forms. The new CO-insertion products represent stable iridacyclobutenones which are reluctant to undergo further insertion reactions involving carbon monoxide, tert-butylisocyanide or dimethylacetylenedicarboxylate. Addition of dimethylacetylendicarboxylate to cluster mixtures containing predominantly [Ir2Rh(μ-PPh2)3(CO) 5] and [Ir3(μ-PPh2)3(CO)6] results in selective reaction at the tri-iridium cluster which allowed for the isolation of the heterometallic cluster by chromatography. In contrast to the tri-iridium parent, [Ir2Rh(μ-PPh2)3(CO) 5] is much less reactive to dimethylacetylendicarboxylate and inert to CO. Similarly, the heterometallic [Ir2Rh(μ-PPh2) 3(CO)4(RNC)3] (R = tert-butyl; 1,1,3,3-tetramethylbutyl) are reluctant to undergo oxidative addition reactions with dimethylacetylendicarboxylate and iodomethane which readily afford addition products with the homometallic parent clusters. The kinetic difference is a consequence of electronic rather than steric factors in the clusters. / Graduate

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A simple and widely applicable method for the synthesis of technetium nitrosyl complexes containing either [99Tc] or [99mTc] has been developed using hydroxylamine as a reducing agent. A number of readily available complexes such as [TcO4]- or [TcX6]2- (X = Cl, Br, I) may be employed as the starting material.

Prévoir la transition laminaire-turbulent de la couche limite sur l'avant-corps d'un véhicule hypersonique est importantpour optimiser l'entrée d'air du superstatoréacteur qui lui est associé, mais reste très difficile après un demi-siècle derecherches intensives sur le sujet. Dans ce travail, les approches numériques et expérimentales sont mises en oeuvre etcomparées. Expérimentalement, la transition naturelle est détectée à Mach 4 et Mach 6 dans la soufflerie continue T-313de l'ITAM à Novossibirsk à l'aide de mesures de pression Pitot. Dans une autre soufflerie de l'ITAM, la AT-303 à rafale,on a détecté la transition naturelle à Mach 6 et la transition déclenchée par rugosités à Mach 8 à l'aide d'un procédéoptique basé sur l'emploi de peintures thermosensibles. Ces essais ont été réalisés sur maquette à échelle 1/3. Toutesles rugosités testées se sont montrées efficaces. La prévision théorique de la transition naturelle a été réalisée au moyende la théorie de la stabilité linéaire locale modale couplée à la méthode du eN. En vol, sur avant-corps à échelle 1, lesfacteurs N atteignent difficilement 8 à 9, ce qui est insuffisant pour assurer la transition avec certitude. Pour appliquer laméthode aux essais au sol, on a besoin de connaître les facteurs N de transition des souffleries, ce qui est réalisé à partird'essais de calibration sur plaque plane dans T-313. Un excellent accord théorie/expérience est obtenu à Mach 4. AMach 6, on doit prendre en compte la présence d'instabilité ‘’crossflow’’ inflexionnelle au nez de l'engin, moyennant quoil'accord est aussi très bon. Les calculs de stabilité ont été réalisés sur des solutions de base obtenues par simulationnumérique (CFD) des conditions de vol ou des essais au sol. Ces simulations ont également permis de bien comprendrela structure de l'écoulement autour de l'avant-corps et de concevoir en grande partie les moyens d'essai. / The prediction of the laminar-turbulent transition in the boundary layer on a hypersonic vehicle forebody is important tooptimize the air inlet of the associated scramjet engine, but is still very difficult after half a century of intensive research onthe subject. In this work, numerical and experimental approaches are applied and compared. Experimentally, the naturaltransition is detected at Mach 4 and Mach 6 in the blow down wind tunnel T-313 in ITAM Novosibirsk using Pitot pressuremeasurements. In the impulse AT-303 wind tunnel in ITAM, the natural transition at Mach 6 and the roughness inducedtransition at Mach 8 are detected using an optical method based on thermosensitive paints. These tests have beenperformed on a 1/3 scale model. All the trips tested have shown their effectiveness. The theoretical prediction of thenatural transition has been performed using the local modal linear stability theory coupled with the eN method. In flight, onthe full scale forebody, N factors hardly reach 8 to 9, which is insufficient for the transition. To apply the method to groundtests, the wind tunnels transition N factors are needed. They are obtained from calibration tests on a flat plate in T-313. Avery good agreement with experiments is found at Mach 4. At Mach 6, the presence of inflexional crossflow instabilitynear the nose of the body must be taken into account, which gives also a good agreement. Stability calculations havebeen done for mean flow solutions obtained by numerical simulations (CFD) of flight or ground tests conditions. Thesesimulations have also helped to understand the structure of the flow around the forebody and to design efficiently theexperimental setup.

Keerthana Samala, for the Master of Science degree in Electrical and Computer, presented on 05/11/2018, at Southern Illinois University Carbondale. TITLE: Test Pattern Generation for Double Transition Faults MAJOR PROFESSOR: Dr. Spyros Tragoudas Under double transition fault model, a fault is associated with a pair of lines and a pair of transitions on these lines. The proposed double transition fault model includes set of cases where the increased delay of a single faulty line may be too small to cause the faulty behavior of the circuit. However, when this delay propagates through another faulty line then the total delay is assumed to be beyond the specified circuit delay which may cause the circuit to fail, thus causing a double transition fault. We propose a test generation procedure for double transition faults, considering different cases of the model. For this purpose a PODEM based Automatic Test Pattern Generation Tool was modified and used. We present experimental results of this procedure for several ISCAS '85 and ISCAS'89 benchmark circuits.

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