A homologous series of regioselectively tetradeprotonated group 8 metallocenes: New inverse crown ring compounds synthesized via a mixed sodium-magnesium tris(diisopropylamide) synergic base

被引:86
作者
Andrikopoulos, PC
Armstrong, DR
Clegg, W
Gilfillan, CJ
Hevia, E
Kennedy, AR
Mulvey, RE [1 ]
O'Hara, CT
Parkinson, JA
Tooke, DM
机构
[1] Univ Strathclyde, Dept Pure & Appl Chem, Glasgow G1 1XL, Lanark, Scotland
[2] Univ Newcastle, Sch Nat Sci Chem, Newcastle Upon Tyne NE1 7RU, Tyne & Wear, England
关键词
D O I
10.1021/ja0472230
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Subjecting ferrocene, ruthenocene, or osmocene to the synergic amide base sodium-magnesium tris(diisopropylamido) affords a unique homologous series of metallocene derivatives of general formula [{M(C5H3)(2)}Na4Mg4(i-Pr2N)(8)] (where M = Fe (1), Ru (2), or Os (3)). X-ray crystallographic studies of 1-3 reveal a common molecular "inverse crown" structure comprising a 16-membered [(NaNMgN)(4)](4+) "host" ring and a metallocenetetraide [M(C5H3)(2)](4-) "guest" core, the cleaved protons of which are lost selectively from the 1, 1', 3, and 3'-positions. Variable-temperature NMR spectroscopic studies indicate that 1, 2, and 3 each exist as two distinct interconverting conformers in arene solution, the rates of exchange of which have been calculated using coalescence and EXSY NMR measurements.
引用
收藏
页码:11612 / 11620
页数:9
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