The synthesis and study of group 13 element-transition metal complexes
Johnston, Thomas Richard
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Reactions of indium(I) chloride with low-valent transition metal carbonyl compounds were shown to have only limited utility for producing indium-transition metal bonds. However, the reaction of indium(I) chloride with triruthenium dodecacarbonyl resulted in the synthesis and structural characterization of a new ruthenium carbonyl complex, Ru2(µ-Cl)2(µ-CO)(THF)2(CO)4 (THF = tetrahydrofuran), which contains coordinated tetrah>drofuran. The information gathered from these reactions indicated that indium-transition metal bonds might be formed if indium(I) chloride reacted with low-valent transition metal carbonyls that contain loosely coordinated solvent ligands. These reactions lead to the preparation of two new indiumtransition metal complexes, [(CH3)3NCH2Cl]3[Ru3(µ-InCl3)(µ-InCl2)(µ-CO)(CO)9l(CH3CN)(CH2Cl2)(l)and [(CH3)3NCH2Cl]2[Os(lnCl3)2(CO)4] (2). The crystal structure of 1 showed that the complex contains both the shortest and longest ruthenium-indium bonds yet reported, at 2.592(2) (A) and 2.793(1) (A), respectively. Another interesting feature of this compound is the coordination of InCl3 to two ruthenium atoms. Compound 2 contains the first reported bond between osmium and a Group 13 element other than boron. A reaction of Na2Fe(CO)4 with GaCl3 produced a new iron-gallium compound, Fe[GaCl2(THF)]2(CO)4, which was characterized by X-ray crystallography. The mechanism for this reaction was studied in order to gain a better understanding of the intermediates that are formed. These studies led to the supposition that a solventstabilized Fe(CO)4 fragment is an intermediate species in the reaction. A new method to produce activated indium metal via the disproportionation of indium(I) chloride in tetrahydrofuran was developed. The activated indium metal then reacted with Fe3(CO)i2 to give [Fe(CH3CN)6]2[Fe7ln2(CO)4o](CH3CN)2. The structure of this complex was determined by X-ray crystallography.