The isolable 16-electron half-sandwich Os complex [OsBr(η5-C5Me5)(PiPr3)] has been synthesized and structurally characterized. This unsaturated complex binds N2 reversibly at low temperature as determined by IR and multinuclear NMR spectroscopy. The reactions of the title complex with CO, H2, PhSiH3, and its thermolysis in C6H6 are reported.
We consider the problem of finding optimum force closure grasps of two and three-dimensional objects. Our focus is on grasps which are useful in practice, namely grasps with a small number of fingers, with friction at the contacts. Assuming frictional contact and rounded finger tips-very mild assumptions in practice-we give new upper (and lower) bounds on the number of fingers necessary to achieve force closure grasps of 2-D and 3-D objects. We develop an optimality criterion based on the notion of decoupled wrenches, and use this criterion to derive optimum two and three finger grasps of 2-D objects, and optimum three finger grasps for 2-D objects. We present a simple O(n) algorithm for computing these optimum grasps for convex polygons, a O(n log n) algorithm for nonconvex polygons, and an O(n/sup 3/) algorithm for polyhedra. In studying these optimum grasps, we derive several interesting theoretical results concerning grasp geometry.< <ETX xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">></ETX>
Abstract We report an approach to conducting the hydroaminomethylation of diverse α‐olefins with a wide range of alkyl, aryl, and heteroarylamines at relatively low temperatures (70–80 °C) and pressures (1.0–3.4 bar) of synthesis gas. This approach is based on simultaneously using two distinct catalysts that are mutually compatible. The hydroformylation step is catalyzed by a rhodium diphosphine complex, and the reductive amination step, which is conducted as a transfer hydrogenation with aqueous, buffered sodium formate as the reducing agent, is catalyzed by a cyclometallated iridium complex. By adjusting the ratio of CO to H 2 , we conducted the reaction at one atmosphere of gas with little change in yield. A diverse array of olefins and amines, including hetreroarylamines that do not react under more conventional conditions with a single catalyst, underwent hydroaminomethylation with this new system, and the pharmaceutical ibutilide was prepared in higher yield and under milder conditions than with a single catalyst.
This paper briefly explores the roles of empiricism and determinism in science and engineering. From this analysis, I conclude that the intellectual exercise that we call “science” is best described as the transition from empiricism (i.e., from what we can observe) to determinism, which is the philosophy that the future can be predicted from the past on the basis of the natural laws that are condensations of all previous scientific knowledge. Thus, “science” is enacted by formulating theories to explain the observations and models, based on those theories, are developed to predict new phenomena. Accordingly, models are the computational arms of theories. Importantly, all models must possess a theoretical basis but not all theories need to predict. The structure of a deterministic model is that it must contain an input, a model “engine”, and an output, that are all linked by a feedback loop that permits the continual updating of the model parameters and a means of assessing predictions against new observations. This latter feature, in essence, enables the application of the “scientific method” of cyclical modification/assessment that continues until the model no longer accounts for new observations. At that point, the model (and possibly the theory, as well) must be discarded and a new theory/model developed. Again, importantly, no amount of successful prediction can “prove” a theory/model to be “correct”, because theories and models are merely the figments of our imagination as developed through imperfect senses and imperfect intellect. Accordingly, all theories and models are wrong at some level of detail. Contrariwise, a single failure of a model to predict an observation invalidates the theory/model unequivocally. The principal impediment to model building is complexity and it is the reason why a compromise must always be made between physical reality and mathematical tractability.
Glassy carbon electrodes were modified by electrochemical reduction of a diazonium molecule ((i)Pr3SiOCH2C6H4N2(+)BF4(-)) featuring a triisopropylsilyl-protected benzylic hydroxyl group. This electrochemical process introduced a monolayer of (i)Pr3SiOCH2C6H4- groups onto the surface of the electrode. The bulky -Si(i)Pr3 protecting group not only prevents the uncontrolled growth of structurally ill-defined and electronically blocking polyphenylene multilayers, but also separates the phenyl groups in the monolayer. Thus, the void spaces between these aryl units should allow a better accommodation of sizable molecules. Removal of the -Si(i)Pr3 protecting groups by (n)Bu4NF exposed the reactive benzylic hydroxyl functionalities that can undergo further transformations to anchor functional molecules. As an example, redox-active ferrocene molecules were grafted onto the modified electrode via a sequence of mesylation, azidation, and copper-catalyzed [3 + 2] cycloaddition reactions. The presence of ferrocenyl groups on the surface was confirmed by X-ray photoelectron spectroscopic and electrochemical studies. The resulting ferrocene-modified glassy carbon electrode exhibits cyclic voltammograms typical of surface-bound redox active species and remarkable electrochemical stability in an acidic aqueous environment.