110795-50-1Relevant academic research and scientific papers
Triple-Decked Complexes, V. - The Mechanism of the Nucleophilic Degradation of μ5-(1-Phenylborole)bis5-(1-phenylborole)rhodium>
Herberich, Gerhard E.,Bueschges, Ulrich
, p. 615 - 620 (2007/10/02)
Reversible nucleophilic degradation of the triple-decked complex Rh2(C4H4BPh)3 (1) with small and basic phosphanes (e.g.PEt3) and amines (e.g.NH3) L produces salts (4) while bulky and/ or less basic nucleophiles (e.g.PiPr3, PCl3 and NHEt2, PhNH2) do not react.The hybrido complex (C4H4BPh)Rh (5) is formed in the system 1/NH3/NMe4Cl/K.The nucleophilic degradation follows a second-order rate law, being first-order in both 1 and L; activation parameters and equilibrium constants were determined for L = PMe3, PEt3 and P(OMe)3.An associative mechanism is proposed.The rate-determining step is a lateral nucleophilic attack at one of the metal centres with concomitant slippage from η5- to η3-bonding; this is then followed by fast addition of two further ligand molecules. - Keywords: Triple-decker complexes/ Nucleophilic degradation/ 1H-Borole/ (1-Phenylborole)rhodium complexes
DERIVATE DES BOROLS VII. (η5-BOROL)RHODIUM-KOMPLEXE UND NUCLEOPHILER ABBAU VON μ-(η5-1-PHENYLBOROL)-BIS5-1-PHENYLBOROL)RHODIUM>
Herberich, G. E.,Bueschges, U.,Hessner, B.,Luethe, H.
, p. 13 - 26 (2007/10/02)
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 = CNBut).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.
