Expanding Heteroscorpionates. Facile Synthesis of New Hybrid Scorpionate/Cyclopentadienyl Ligands and Their Lithium and Group 4 Metal Compounds: A Combined Experimental and Density Functional Theory S

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• 作者：Antonio Otero ; Juan Fern&aacute ; ndez-Baeza ; Antonio Antiñ ; olo ; Juan Tejeda ; Agustí ; n Lara-S&aacute ; nchez ; Luis F. S&aacute ; nchez-Barba ; Margarita S&aacute ; nchez-Molina ; Ana M. Rodrí
• 刊名：Organometallics
• 出版年：2007
• 出版时间：August 13, 2007
• 年：2007
• 卷：26
• 期：17
• 页码：4310 - 4320
• 全文大小：226K
• 年卷期：v.26,no.17(August 13, 2007)
• ISSN：1520-6041

文摘

The preparation of new hybrid scorpionate/cyclopentadienyl ligands in the form of the lithium derivatives[Li(bpzcp)(THF)] (1) [bpzcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1,1-diphenylethylcyclopentadienyl] and[Li(bpztcp)(THF)] (2) [bpztcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-tert-butylethylcyclopentadienyl] oras a mixture of the two scorpionate/cyclopentadiene regioisomers (bpzpcpH) 1-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1-phenylethyl]-1,3-cyclopentadiene (3a) and 2-[2,2-bis(3,5-dimethylpyrazol-1-yl)-1-phenylethyl]-1,3-cyclopentadiene (3b) has been carried out by reaction of bis(3,5-dimethylpyrazol-1-yl)methane(bdmpzm) with BuⁿLi and 6,6-diphenylfulvene, 6-tert-butylfulvene, or 6-phenylfulvene, respectively.However, when this insertion reaction was carried out with 6,6-dimethylfulvene, the compound [Li(^isoprcp)(bdmpzm)(THF)] (4) [^isoprcp = isopropenylcyclopentadienyl] was obtained. Compounds 1 and 2 reactedwith [TiCl₄(THF)₂] or [MCl₄] (M = Zr, Hf) to give the complexes [MCl₃(bpzcp)] (M = Ti, 5; Zr, 6; Hf,7) and [MCl₃(bpztcp)] (M = Ti, 8; Zr, 9; Hf, 10). Similar reactions do not take place with the mixtureof the two isomers 3a and 3b. However, when a THF solution of 3a-3b and [MCl₄] (M = Zr, Hf) washeated under reflux, the complexes [MCl₃(bpzpcp)] (M = Zr, 11; Hf, 12) [bpzpcp = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-phenylethylcyclopentadienyl] were obtained. In addition, alkyl complexes[ZrClMe₂(bpztcp)] (13) and [ZrMe₃(bpztcp)] (14) were also prepared. The structures of these complexeshave been determined by spectroscopic and DFT methods, and in addition, the X-ray crystal structuresof 1, 2, 3b, and 6 were also established.