Phosphorus-31 solid-state NMR studies of cyclic and acyclic phosphine-metal complexes. Determination of chemical shift anisotropy, scalar coupling sup 1 J sub M-P (M = sup 55 Mn, sup 95/97 Mo, sup 183 W), and sup 55 Mn quadrupolar coupling constants
- Inst. fuer Anorganische Chemie der Univ., Tuebingen (West Germany)
Cp(OC){sub 2}ClW (2), Cp(OC){sub 2}MeW (3); R = Et (a), Pr (b), Bu (c), Pe = Pentyl (d) and (M)PPh{sub 2}(CH{sub 2}){sub n} ((M) = (OC){sub 4}Mn (4), Cp(OC){sub 2}W (5), Cp(OC){sub 2}Mo (6); n = 3 (b), 4 (c); (M) = (OC){sub 4}MnSO{sub 2} (7); n = 2 (b), 3 (c), 4 (d)) are determined by solid-state NMR techniques and correlated to structural features of the compounds. In general the isotropic chemical shift in the solid-state was found to be of the same order as the chemical shift in solution. There are differences in the tensor components due to structural changes for the manganese complexes 1. Different bond weakening abilities of a ligand (trans influence) in complexes 2 and 3 cause a large change of only one tensor component, while the other components remain constant. A crossover of the center shielding tensor component and the low-field component is observed for the five- and six-membered rings 4b-7b and 4c-7c, respectively. {sup 55}Mn- and {sup 95/97}Mo-{sup 31}P coupling constants have been observed that are not obtainable in solution. The different spacings within the multiplets of the {sup 31}P CP/MAS spectrum of the manganese complex 1d allows the authors to estimate the quadrupolar coupling constant {chi} and the asymmetry parameter {eta} of the electric field gradient at manganese.
- OSTI ID:
- 5900257
- Journal Information:
- Inorganic Chemistry; (United States), Vol. 30:5; ISSN 0020-1669
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
HETEROCYCLIC COMPOUNDS
CHEMICAL SHIFT
MANGANESE COMPLEXES
MOLYBDENUM COMPLEXES
PHOSPHINES
TUNGSTEN COMPLEXES
EXPERIMENTAL DATA
MANGANESE 55
MOLYBDENUM 95
MOLYBDENUM 97
NMR SPECTRA
PHOSPHORUS 31
TUNGSTEN 183
COMPLEXES
DATA
EVEN-ODD NUCLEI
HEAVY NUCLEI
INFORMATION
INTERMEDIATE MASS NUCLEI
ISOMERIC TRANSITION ISOTOPES
ISOTOPES
LIGHT NUCLEI
MANGANESE ISOTOPES
MOLYBDENUM ISOTOPES
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
PHOSPHORUS COMPOUNDS
PHOSPHORUS ISOTOPES
RADIOISOTOPES
SECONDS LIVING RADIOISOTOPES
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
TUNGSTEN ISOTOPES
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation