Studies of Reactive Organic Ions in the Gas Phase

一种新的双电池傅里叶变换离子回旋共振(FT-ICR)装置将被用来获得一些当前感兴趣的离子的详细机制、动力学和热化学信息。将研究三个领域：(1)自由基阳离子的双分子反应，其中电荷和自由基位置是分开的(远离子离子)；(2)重氮离子的无溶剂反应的稳定性和反应性，这是有机化学中的重要中间体；(3)双配位磷阳离子(膦离子)的结构、化学性质和稳定性。这也将产生各种有趣的中性、缺电子的磷化合物的生成热。来自有机动力学项目的这笔赠款支持普渡大学希尔卡·I·肯塔玛博士的研究。通过用电子轰击分子，气相中会产生带正电荷的离子。这些离子将在一个特别设计的电池中被捕获不同的时间段，这样它们的反应就可以作为时间的函数进行检查。通过这种方法，这些反应进行的速度和这些不寻常离子在气相中的能量将被确定。将在气相和溶液中对其中一些反应进行比较，以确定溶剂分子的影响。

A new dual-cell Fourier transform ion cyclotron resonance (FT-ICR) device will be used to obtain detailed mechanistic, kinetic, and thermochemical information for a number of ions of current interest. Three areas will be investigated: (1) bimolecular reactions of radical cations, where the charge and radical sites are separated (distonic ions); (2) the stability and reactivity of solvent-free reactions of diazonium ions, which are important intermediates in organic chemistry; and (3) the structure, chemical properties, and stabilities of dicoordinated phosphorous cations (phosphenium ions). This will also yield heats of formation for various interesting neutral, electron-deficient phosphorous compounds. %%% This grant from the Organic Dynamics Program supports the research of Dr. Hilkka I. Kenttamaa at Purdue University. Positively charged ions will be generated in the gas-phase by bombarding molecules with electrons. These ions will be trapped for various periods of time in a specially designed cell, so that their reactions can be examined as a function of time. By this means, the rate at which these reactions proceed and the energy of these unusual ions in the gas-phase will be determined. Comparisons will be made between some of these reactions in the gas-phase and in solution to determine the effect of solvent molecules.