A kinetic study of the reactions of Group VI-B hexacarbonyls with primary amine and halide ligands was undertaken in order to determine the possible mechanisms of these reactions. As well as the expected dissociative pathway, the reactions with the primary amines were seen to proceed by a concurrent pathway which was dependent upon the ligand concentration. Since nitrogen donor ligands are expected to be poor donor ligands, the mechanism proposed was a "dissociative interchange" mechanism which should not be too dependent upon the nucleophilicity of the ligand. Comparison of the rate constants for the amines studied as well as those of the previously investigated Lewis base ligands indicated all such reactions may proceed through the same mechanism. The similarity in rate constants for the ligand-independent and ligand-dependent pathways supports this mechanism. The rate of formation of the final product was seen to be dependent upon the square of the mercuric halide concentration. Therefore, the conversion of Fe(CO)4(HgX)2 to the final product was proposed to proceed by the successive abstraction by each HgX group of two molecules of mercuric halide. These oxidative elimination reactions are related to a chemical model for the intermediate step in the reduction of dinitrogen to ammonia …

In model reaction systems to test amino acids in chlorinated waste effluents, several amino acids were chlorinated at high chlorine doses. (2000-4000 mg/1). Amino acids present in municipal waste effluents before and after chlorination were concentrated and purified using cation exchange and Chelex resins. After concentration and cleanup of the samples, the amino acids were derivatized by esterification of the acid functional groups and acylation of the amine groups. Identification and quantification of the amino acids and chlorination products was carried out by gas chromatography/mass spectrometry, using a digital computer data system. Analysis of the waste products revealed the presence of new carbon-chlorine bonded derivatives of the amino acid tyrosine when the effluents were treated with heavy doses of chlorine.

This investigation deals with the preparations of cyclic organosilanes via two different types of organometallic precursors: borane adducts to chlorovinylsilanes and tertbutyllithium adducts to chlorovinylsilanes. The regiospecificity of the hydroboration of various types of boranes to chlorovinylsilanes was studied by three different methods. It was found that, by using bulky hydroborating agents, about 80% isomerically pure terminal borane adducts to chlorovinylsilanes could be obtained. While the adducts are potential precursors to silacyclopropanes, when these borane adducts were treated with bases such as sodium methoxide and methyl Grignard, no evidence for silacyclopropane formation was found.

A model system to calculate single-path coupling constant was devised to see if the couplings are additive in a system which has a dual-pathway. The system chosen was o-methyl-13C-benzoic acid. Because of anomalies in the data, the series was extended. Hybridization of the label appeared to have relatively little effect, and the conformation of the substituents very important.