Synthesis, Structure, Electrochemistry, and Metal‐Atom Dynamics of Cyclopentadienyl Ferracarboranes

Abstract

A series of metallacarboranes, incorporating the CpFe fragment, were studied by electrochemical techniques, temperature-dependent Mössbauer effect (ME) spectroscopy, and Xray diffraction. The compounds studied include the parent dicarbollide complex CpFeC 2 B 9 H 11 (1) and its reduced form , and 2b were investigated by X-ray diffraction. The ME spectroscopic study elucidated the relationship between the nature of the five-membered carborane face coordinated to the me-

Metal atom dynamics in organometallics: Cyano ferrocenes

“…Compound 4 [2] as well as compounds 2, 3, 5, and 6 [8] were prepared using literature methods. (b) Mö ssbauer spectroscopy (MES): The air stable solids were ground with Pyrex powder and mixed with BN to ensure random crystallite orientation in the subsequent MES measurements, transferred to Perspex sample holders, and mounted in a cryostat in transmission geometry as previously described [3][4][5][6]. Spectrometer calibration was effected with a-Fe and all isomer shifts are referred to the centroid of such room temperature calibration spectra.…”

“…An improved mercury-free synthesis of the previously poorly characterized tricyanovinyl ferrocene has been reported [2] and its crystal structure has been determined at 173 and 293 K. As has been shown in numerous examples in the recent literature [3][4][5][6], temperature-dependent Mö ssbauer effect spectroscopy (MES) can further help to elucidate the metal atom dynamics in ferrocenoid solids, and the present investigation was undertaken to examine the effect of ring substituent electronic and steric effects on the motional characteristics of the metal atom in a number of closely related cyano ferrocenes.…”

Cationic metallacarborane species [(Carb)M]+: generation and synthetic application

“…In particular, the visible light irradiation of this complex in the presence of the anion [Carb´] -affords ferracarborane CpFeCarb´ 8. We found that the benzene ligand in the cation [Carb´Fe(C 6 H 6 )] + is easily replaced with the two electron ligands Bu t CN and P(OR)3 to give the complexes [Carb´FeL 3 ] + (Scheme 6).…”

(Tetramethylcyclobutadiene)cobalt complexes 10. Synthesis of arene complexes [(C4Me4)Co(arene)]+ and mechanism of the arene exchange reaction

“…5 Development of this method al lowed one to obtain half sandwich, sandwich, and triple decker complexes, as well as metallacarboranes and clus ters containing the CpFe fragment. [6][7][8][9][10][11] The Cb*Co (Cb* = C 4 Me 4 ) and CpFe fragments are isolobal, which allows one to expect similar chemical behavior for their derivatives. 12 The iodide complex Cb*Co(CO) 2 I (1) was synthesized by the transfer of the cyclobutadiene ligand from the nickel halide complexes [Cb*NiX 2 ] 2 (X = Cl, I).…”