141293-50-7Relevant articles and documents
Derivatives of Borole, XVIII. - Tricarbonyl5-(1-phenylborole)>iron: Reactivity of the Coordinated Ligands
Herberich, Gerhard E.,Carstensen, Tobias,Klaff, Norbert,Neuschuetz, Mark
, p. 1801 - 1806 (2007/10/02)
The borole complex (C4H4BPh)Fe(CO)3 (1) undergoes Friedel-Crafts acetylation (MeCOCl/AlCl3) at the meta-position of the phenyl substituent while the derivatives (C4H4BPh)Fe(CO)2L (3, a: L=NMe3, b: L=PMe3) are acetylated at the 2-position of the borole ring.Organolithium reagents (LiMe, LiBu) add to 1 at the boron atom below -50 deg C while nucleophilic attack at the carbonyl C atom takes place at higher temperatures with formation of acyl anions - (6a,b-).The Fischer carbene complex (C4H4BPh)Fe(CO)2 (7) is obtained from 6a-/BF4.Complex 1 reacts with LiN(SiMe3)2 to give - (8-) and with 5 M NaOH/C6H6/NBu4HSO4 to produce the hydride NBu4 (NBu4*9).A highly reactive dianion 2- (102-) is obtained by deprotonation of 9- or by reduction of 1 or 3a in THF at -70 deg C.Treatment of 102- with Ph3SnCl gives - (11-) which is isolated as NEt4*11.Slow reduction of 3a with sodium amalgam in THF at -30 deg C produces doubly CO-bridged cis-2- (122-) which is deprotonated to the μ2-hydrido anion - (13-). Key Words: (Borole)carbonyliron derivatives, electrophilic substitution, nucleophilic addition, reduction/ Iron complexes