Studies of Highly Reactive Molecules and Intermediates

有机合成计划将支持保罗·g·加斯曼博士继续进行研究。Gassman博士将继续他对高应变体系的富有成效的研究，并开始过渡金属配体的合成工作。这些将被用来改变金属的表面氧化状态。这种对氧化态的控制将促进我们经济所需的日益复杂的材料的合成。有机金属化学领域的研究将集中在使用x射线光电子能谱（XPS）来了解配体对络合过渡金属的电子影响。将制备出比现有配体更具吸电子性或给电子性的新配体。计划制备和研究可作为氧化剂或还原剂的配合物的性质作为附着配体的函数。我们将继续研究trans-bicycloın.1.0！烷烃，张力副环烷，和张力环上的电子转移。探索电化学还原的新合成应用。将寻求改进激发态氧化剂的方法，以发展对简单烯烃亲核试剂反马尔可夫尼科夫加成的合成有用的程序。自由基，阴离子自由基，阳离子自由基和阳离子的研究将进行。

The Organic Synthesis Program will support the continuation of the research of Dr. Paul G. Gassman. Dr. Gassman will continue his productive studies on highly strained systems and initiate work on the synthesis of ligands for transition metals. These will be used to change the apparent oxidation state of the metal. This increased control of the oxidation state will facilitate the synthesis of the increasingly complex materials needed by our economy. Studies in the area of organometallic chemistry will be centered on the use of X-ray photoelectron spectroscopy (XPS) to understand the electronic influence of ligands on complexed transition metals. New ligands will be prepared which are either more electron withdrawing or electron donating than currently available ligands. It is planned to prepare and study the properties of complexes which can serve as either oxidants or reductants as a function of the attached ligands. Work will continue on studies of trans-bicycloın.1.0!alkanes, strained paracyclophanes, and electron transfer from strained rings. New synthetic applications of electrochemical reductions will be explored. Improved excited state oxidants will be sought in an approach to the development of synthetically useful procedures for anti-Markovnikov addition of nucleophiles to simple olefins. Studies of radicals, anion radicals, cation radicals and cations will be carried out.