Derivate des Borols, XVIII. Tricarbonyl[η5-(1-phenylborol)]eisen: Zur Reaktivität der koordinierten Liganden
✍ Scribed by Herberich, Gerhard E. ;Carstensen, Tobias ;Klaff, Norbert ;Neuschütz, Mark
- Publisher
- Wiley (John Wiley & Sons)
- Year
- 1992
- Tongue
- English
- Weight
- 556 KB
- Volume
- 125
- Category
- Article
- ISSN
- 0009-2940
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✦ Synopsis
The borole complex (C4H4BPh)Fe(C0)3 (1) undergoes Friedel-Crafts acetylation (MeCOC1/AlC13) at the meta-position of the phenyl substituent while the derivatives (C4H4BPh)Fe(C0)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°C while nucleophilic attack at the carbonyl C atom takes place at higher temperature with formation of acyl anions [(C,H,BPh)Fe(CO),(COR)]-(6a,b-). The Fischer carbene complex (C,H,BPh)Fe(CO),[C(OMe)Me] (7) is obtained from 6a-/[Me30]BF4 Complex 1 reacts with ~ ~ ~ ~~~~~ lorole)]iron: Reactivity of the Coordinated Ligands LiN(SiMe3)2 to give [(C,H,BPh)Fe(CO),(CN)]-( 8 -) and with 5 M NaOH/C6H6/NBu,HS04 to produce the hydride NBu4-[(C4H4BPh)FeH(C0)2] (NBu, . 9). A highly reactive dianion [(C4H4BPh)Fe(C0),12-(loz-) is obtained by deprotonation of 9-or by reduction of 1 or 3a in THF at -70°C. Treatment of 10'-with Ph3SnC1 gives [(C4H,BPh)Fe(CO),(SnPh3)]-(11-) which is isolated as NEt4 . 11. Slow reduction of 3a with sodium amalgam in THF at -30°C produces doubly CO-bridged C ~~-[ { ( C ~H ~B P ~) F ~( C O ) ~~~] ~-(12*-) which is protonated to the pz-hydrido anion [p-H-{(C4H4BPh)Fe(CO)z)z] -(13-).
Die Chemie der Borol-Metall-Komplexe ist in den letzten Jahren vielfaltig g e ~o r d e n ~~, ~] .
Dennoch sind nur wenige Befunde zur Reaktivitat der koordinierten Borol-Liganden bekannt. Wir haben deshalb eine systematische Untersuchung eines besonders gut zuganglichen Borol-Komplexes, des Tricarbonyl[q'-( 1 -phenylborol)]eisens, (C4H4BPh)Fe(C0)3 (1)[5361, unternommen und berichten hier iiber dessen Reaktivitat.