Aluminum complexes incorporating bulky nitrogen and sulfur donor ligands
- Univ. of Iowa, Iowa City, IA (United States). Dept. of Chemistry
- Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry
The synthesis and structures of aluminum complexes incorporating bulky thioamidate (RC(NR{prime})S{sup {minus}}), thioureido (R{prime}HNC(NR{prime})S{sup {minus}}), and amidinate (RC(NR{prime}){sub 2}{sup {minus}}) ligands are described. The reaction of AlMe{sub 3} with and{double_bond}C{double_bond}S (Ad = 1-adamantyl) affords the insertion product {l_brace}MeC(and)S{r_brace}AlMe{sub 2} (1), which binds 1 equiv of AlMe{sub 3} to generate {l_brace}MeC(and)S{r_brace}AlMe{sub 2}{center_dot}AlMe{sub 3} (2). The alkane elimination reaction of AlMe{sub 3} and N,N{prime}-disubstituted thiourea derivatives, (R{prime}HN){sub 2}C{double_bond}S, affords thioureido complexes {l_brace}R{prime}HNC(NR{prime})S{r_brace}AlMe{sub 2} (3a, R{prime} = Ad; 3b, R{prime} =Ar = 2,6-{sup i}Pr{sub 2}-Ph). Carbodiimides, R{prime}N {double_bond}C{double_bond}NR{prime}, react with AlMe{sub 3} to afford acetamidinate compounds {l_brace}MeC(NR{prime}){sub 2}{r_brace}AlMe{sub 2} (4a, R{prime} = Ad; 4b, R{prime} = Ar). Sequential addition of {sup t}BuLi and AlX{sub 2}Cl (X = Cl, Me) to R{prime}N{double_bond}C{double_bond}NR{prime} affords pivamidinate compounds {l_brace}{sup t}BuC(NR{prime}){sub 2}{r_brace}AlCl{sub 2} (5b, R{prime} = Ar) and {l_brace}{sup t}BuC(NR{prime}){sub 2}{r_brace}AlMe{sub 2} (6a, R{prime} = Ad; 6b, R{prime} = Ar). Complexes 1, 3a, 6a, and 6b have been characterized by X-ray crystallography.
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- FG02-88ER13935
- OSTI ID:
- 655338
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 18 Vol. 17; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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