X-ray diffraction, Raman spectroscopic, and solid-state NMR studies of the group 14 metal-(tetracarbonyl)cobalt complexes Ph3MCo(CO)4(M = Si, Sn, Pb)

Abstract

Single-crystal X-ray diffraction studies illustrate that the three title compounds are isomorphous, belonging to the triclinic space group P[Formula: see text], with slightly distorted trigonal bipyramidal geometry about cobalt. The solid-state29Si,119Sn, and207Pb cross-polarization magic angle spinning (CP MAS) NMR spectra are presented. The indirect spin–spin coupling constant (J), quadrupolar–dipolar shift (d), direct dipolar coupling constant (D' ), anisotropy in spin–spin coupling (ΔJ), and the chemical shift tensor were extracted. A plot of the reduced coupling constant vs. s-electron densities at the nucleus indicates that the Fermi contact term may be dominant for the tin and lead complexes; however, the large ΔJ for all complexes indicate that there are also significant anisotropic terms. Trends in the Raman scattering spectra are also discussed.Key words:29Si,119Sn, and207Pb CP MAS NMR, tetracarbonyl cobalt, spin–spin coupling, chemical shift tensor, quadrupole coupling, Fermi contact, cobalt–group 14.