DERIVATE DES BOROLS VII. (η5-BOROL)RHODIUM-KOMPLEXE UND NUCLEOPHILER ABBAU VON μ-(η5-1-PHENYLBOROL)-BIS5-1-PHENYLBOROL)RHODIUM>

Article abstract of DOI:10.1016/0022-328X(86)80275-3

Dehydrogenating complexation of borolenes C4H6BR (R = Me, Ph) with 2-C2H4)2Cl>2 gives the triple-decked complexes μ-L-(RhL)2 (III) with L = η⁵-C4H4BR.Cyclopentadienide degradation of III gives the uncharged complexes CpRhL (IV) and the water-soluble salts Na (Na⁺*V) which are characterized as NMe4⁺ (R = Me) and Cs⁺ salts (R = Ph).In CD2Cl2/CF3CO2D the complex CpRh(η⁵-C4H4BPh) shows fast exchange at the α-position to the boron at 0 deg C, thus providing the first evidence of an electrophilic substitution of an (η⁵-borole)metal complex.Protonation of V gives RhHL2 (VII) as the first (η⁵-borole)metal hydrides.Various neutral nucleophiles effect a valence disproportionation of IIIb (R = Ph) with formation of the compounds (VIII) (Y = PMe3), IX (Y = P(OMe)3), and X(Y = CNBu^t).Cyanide degradation of IIIb in acetonitrile yields K2, characterized as PPh4⁺ salt (XII).Further degradation in aqueous solution provides the anion ^- (XIII) isolated as the ⁺ salt (XIV).Anion XIII constitutes the first Lewis-base adduct of a simple, i.e.C-unsubstituted borole.