title: Ultrahigh-field NMR spectroscopy of quadrupolar transition metals: 55Mn NMR of several solid manganese carbonyls.
abstract: 55Mn NMR spectra acquired at 21.14 T (nu(L)(55Mn) = 223.1 MHz) are presented and demonstrate the advantages of using ultrahigh magnetic fields for characterizing the chemical shift tensors of several manganese carbonyls: eta5-CpMn(CO)3, Mn2(CO)10, and (CO)5MnMPh3 (M = Ge, Sn, Pb). For the compounds investigated, the anisotropies of the manganese chemical shift tensors are less than 250 ppm except for eta5-CpMn(CO)3, which has an anisotropy of 920 ppm. At 21.14 T, one can excite the entire m(I) = 1/2 <--> m(I) = -1/2 central transition of eta5-CpMn(CO)3, which has a breadth of approximately 700 kHz. The breadth arises from second-order quadrupolar broadening due to the 55Mn quadrupolar coupling constant of 64.3 MHz, as well as the anisotropic shielding. Subtle variations in the electric field gradient tensors at the manganese are observed for crystallographically unique sites in two of the solid pentacarbonyls, resulting in measurably different C(Q) values. MQMAS experiments are able to distinguish four magnetically unique Mn sites in (CO)(5)MnPbPh3, each with slightly different values of delta(iso), C(Q), and eta(Q).
authors.affiliation: Department of Chemistry, University of Alberta, Edmonton, Alberta T6G 2G2, Canada.
authors.forename: Kristopher J
authors.initials: KJ
authors.lastname: Ooms
authors.forename: Kirk W
authors.initials: KW
authors.lastname: Feindel
authors.forename: Victor V
authors.initials: VV
authors.lastname: Terskikh
authors.forename: Roderick E
authors.initials: RE
authors.lastname: Wasylishen