Browsing by Subject "Indium compounds"
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Item Preparation and reactions of transition metal-indium mixed metal complexes(Texas Tech University, 1992-08) Lin, Chu-chiehThe primary objective of this research is the syntheses of new complexes containing bonds between transition metals and indium. The secondary objective is to synthesize new compounds containing copper, indium and selenium. A number of transition metal-indium mixed-metal complexes have been synthesized. Their structures have been characterized by single crystal X-ray diffraction as well as other spectroscopic methods. Several compounds containing copper, indium and selenium were also synthesized and characterized. Fe3(CO)l2 reacted with InCl to give |(CO)4Fe(M- InCl(THF))|2 (1) which further reacted with In-Bu)4NBr producing |(n-Bu)4N]2l(CO)4Fe(|Li-InClBr)j2 (2). Fe(C0)4(THF) is believed to be the intermediate in the preparation of compound (1) in all of the following reactions: Fe3(CO)i2 + InCL Na2Fe(CO)4 + InCl3 and Na2Fe2(CO)8 + InCl3. The reaction of |{C0)4Fe{ M-lnCI(THF) 1|2 with NaOR (NaOR: sodium 2.4,6-Tri-ieri-hutyl phenoxide) furnished an uncharacterized compound (3) which further reacted with Ph4PBr to yield |PPh4 l2l(CO)4Fe{)Li-lnCIBr) |2 (4). The reaction of Co4(CO)|2 with InBr in THE at room temperature formed | {(CO)4Co } 2lnm-Br) |2 (5) and |(CO)i2Co4lnKBri2i (6). Co4(CO)l2 reacted with InCI to give |((CO)4Co)2ln(|i-CI)|2 (7) and f(CO)i2Co4ln8Cli2l (8). The reaction of compound (5) with PPh3 gave l{(PPh3)Co(CO)3}InBr2(PPh3)] (9) and [ ((PPh3)Co(CO)3 )2ln(|Li Br)J2 (10). Compound (6) reacted with AsPh3 to give |{(AsPh3)Co(CO)3)InBr2(AsPh3)] (11). The reaction of compound (7) with BzEt3NCl produced IBzEt3Nl2l(CO)i2Co4ln8Cli4(CH3CN)4](12). Ru3(CO)i2 reacted with InCl to yield a cluster which was characterized as |Ru(C0)2ln(THF)|n (where, n > 4) (13) which further reacted with BzEt3NCI to give |Ru(CO)2lnCI(BzEt3N)|n (14). The reaction of (i-Bu)SeSe(t-Bu) with |(C0D)CuCI)|2 produced |( t-Bu )SeSe(t-Bu )(CuCI )2 In (15). (i-Bu)2Se reacted with |(C0D)CuCI)2 to yield a colorless compound which was characterized as | {(t-Bu)2Se }2CuCI |2 (16).Item Preparation of new mixed-metal complexes containing transition metals (Fe, Ru) and group 13 elements (Ga, In)(Texas Tech University, 1993-12) Cho, HyunhoA series of new mixed-metal complexes containing transition metal and Group 13 elements have been synthesized by salt elimination reactions and structurally characterized by single-crystal X-ray diffraction methods. The complex Fe2{|i-lnCI(THF)}2(CO)8 (1) has been prepared in high yield by the reaction of either Na2Fe(CO)4or Na2Fe2(CO)8 with indium tri chloride in tetrahydrofuran. The reaction of Na2Fe(CO)4 with one molar equivalent of gallium trichloride in tetrahydrofuran produced Fe2{^-GaCI(THF)}2(CO)8 (2). This complex can also be prepared, although in very low yield, by a similar reaction between Na2Fe2(CO)8 and gallium trichloride in tetrahydrofuran. Mechanistic studies suggest that a solvent-stabilized Fe(C0)4 fragment Is an intermediate in both iron-indium and iron-gallium reactions. A mixture of Na2Fe(CO)4 and three molar equivalents of gallium trichloride in toluene produced Fe2(^i-GaCI)2(CO)8-4NaCI (3), and Na2Fe2(CO)8 reacts with a large excess of gallium trichlioride in toluene to give compounds Fe2(^i-GaCI)2(CO)8-4NaCI (3), [Fe(CO)4(GaCl2)2]n (4), and the two rotational isomers of the bis-toluene complexes [(Ti6-C6H5Me)2Fe][Na(GaCl4)3] (6) and [(r|6-C6H5Me)2Fe][Na(GaCl4)2][(^l-CI)(GaCl3)2] (7). The reaction of Na2Fe2(CO)8 with AsPha and gallium trichloride in tetrahydrofuran yielded Fe(CO)4(AsPh3), Fe(CO)3(AsPh3)2, and a small amount of [(THF)Na][Fe5(^i3-Ga)2(^i-CI)(^i-CO)4(CO)i6](5).Item The synthesis and study of group 13 element-transition metal complexes(Texas Tech University, 1996-12) Johnston, Thomas RichardReactions 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.