Lithium, Titanium, and Zirconium Complexes with Novel Amidinate Scorpionate Ligands
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- 作者：Antonio Otero ; Juan Ferná ; ndez-Baeza ; Antonio Antiñ ; olo ; Juan Tejeda ; Agustí ; n Lara-Sá ; nchez ; Luis F. Sá ; nchez-Barba ; Isabel Ló ; pez-Solera ; Ana M. Rodrí ; guez
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：March 5, 2007
- 年：2007
- 卷：46
- 期：5
- 页码：1760 - 1770
- 全文大小：413K
- 年卷期：v.46,no.5(March 5, 2007)
- ISSN：1520-510X
文摘
The reaction of bis(3,5-dimethylpyrazol-1-yl)methane (bdmpzm) with BunLi and carbodiimide derivatives, namely,N,N'-diisopropyl, dicyclohexyl, and 1-tert-butyl-3-ethyl carbodiimides, enables the preparation of new heteroscorpionateligands in the form of the lithium derivatives [Li(NNN)(THF)] (NNN = pbpamd (1) (pbpamd = N,N'-diisopropylbis(3,5-dimethylpyrazol-1-yl)acetamidinate); cbpamd (2) (cbpamd = N,N'-dicyclohexylbis(3,5-dimethylpyrazol-1-yl)acetamidinate); and tbpamd (3) (tbpamd = N-ethyl-N'-tert-butylbis(3,5-dimethylpyrazol-1-yl)acetamidinate)), althougha similar process with N,N'-dimethylcarbodiimide gave the dinuclear complex [Li(bpzii)(THF)]2 (4) (bpzii =N-(dimethylamino)-N'-[(dimethylamino)bis(3,5-dimethylpyrazol-1-yl)methylimino]imino). When this last reaction wascarried out in an air atmosphere, the cluster complex [Li8(
f">4-O)2(f">4-OH)2(f">4-pz)2(
fchars/kappa.gif" BORDER=0 >2-bpziLi)2(bpzCN)2(THF)4] (5)(bpziLi = dimethylaminobis(3,5-dimethylpyrazol-1-yl)methyliminolithium, bpzCN = bis(3,5-dimethylpyrazol-1-yl)acetonitrile) was isolated and characterized by X-ray analysis. Finally, when the same process was carried out inthe presence of water the amidine-scorpionate (bpzan) (6) (bpzan = N,N-dimethylbis(3,5-dimethylpyrazol-1-yl)acetamidine) was obtained. Compounds 1 and 3 reacted with [TiCl4(THF)2] or [ZrCl4] to give complexes ofstoichiometry [MCl3((fchars/kappa.gif" BORDER=0 >3-NNN))] (M = Ti, Zr) (7-10). The structures of the different compounds were determined byspectroscopic methods and, in addition, the X-ray crystal structures of 1, 3, 4, 5, and 6 were also established.
f">4-O)2(f">4-OH)2(f">4-pz)2(fchars/kappa.gif" BORDER=0 >2-bpziLi)2(bpzCN)2(THF)4] (5)(bpziLi = dimethylaminobis(3,5-dimethylpyrazol-1-yl)methyliminolithium, bpzCN = bis(3,5-dimethylpyrazol-1-yl)acetonitrile) was isolated and characterized by X-ray analysis. Finally, when the same process was carried out inthe presence of water the amidine-scorpionate (bpzan) (6) (bpzan = N,N-dimethylbis(3,5-dimethylpyrazol-1-yl)acetamidine) was obtained. Compounds 1 and 3 reacted with [TiCl4(THF)2] or [ZrCl4] to give complexes ofstoichiometry [MCl3((fchars/kappa.gif" BORDER=0 >3-NNN))] (M = Ti, Zr) (7-10). The structures of the different compounds were determined byspectroscopic methods and, in addition, the X-ray crystal structures of 1, 3, 4, 5, and 6 were also established.