Linear uranium metallocenes with polydentate aromatic nitrogen ligandsCCDC reference numbers 764413-764415. For crystallographic data in CIF or other electronic format see DOI: 10.1039/c002279a

• Main Authors: Berthet, Jean-Claude, Maynadié, Jérôme, Thuéry, Pierre, Ephritikhine, Michel
• Format: Article
• Language: English
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c002279a

Treatment of [Cp* 2 U(NCMe) 5 ]X 2 [Cp* = C 5 Me 5 , X = BPh 4 ( 1 ) or I ( 1 ′)] or Cp* 2 UI 2 in acetonitrile with the polydentate aromatic nitrogen bases phen, terpy and R 4 btbp led to the formation of the linear uranium metallocenes [Cp* 2 U(NCMe) 3 (phen)]X 2 [X = BPh 4 ( 2 ), I ( 2 ′)], [Cp* 2 U(NCMe) 2 (terpy)][BPh 4 ] 2 ( 4 ), [Cp* 2 U(NCMe)(Me 4 btbp)][BPh 4 ] 2 ( 5 ) and [Cp* 2 U(NCMe)(CyMe 4 btbp)][X] 2 , [X = BPh 4 ( 6 ), I ( 6 ′)], [phen = 1,10-phenanthroline, terpy = 2,2′:6,2′′-terpyridine, Me 4 btbp = 6,6′-bis-(3,3,6,6-tetramethyl-1,2,4-triazin-3-yl)-2,2′-bipyridine, CyMe 4 btbp = 6,6′-bis-(3,3,6,6-tetramethyl-cyclohexane-1,2,4-triazin-3-yl)-2,2′-bipyridine]. The bent metallocene [Cp* 2 U(phen) 2 ][BPh 4 ] 2 ( 3 ) was isolated from the reaction of 1 and two molar equivalents of phen in THF. The X-ray crystal structures of 2 ·2MeCN, 3 ·2THF, 4 and 6 ′·2MeCN were determined. A variety of dicationic uranium( iv ) metallocenes with an unusual linear geometry have been isolated by reaction of neutral bi-, tri-, and tetradentate polynitrogen aromatic molecules (phenanthroline, terpyridine, CyMe 4 btbp) with the dicationic species [Cp* 2 U(NCMe) 5 ]X 2 (Cp* = C 5 Me 5 , X = BPh 4 , I) and structurally characterized.