The synthesis of a variety of monosubstituted manganese and rhenium carbonyl cationic species of the form [M(CO)sL] [PFe] is reported, where L = group 5A ligands. Preparation of these derivatives was accomplished either through the reaction of [LM(CO)4]~w ith C2H5O2CCI followed by treatment with HBF4 (or BF3) or by thermal replacement of CH3CN in the M(CO)5(CH3CN)+ derivative. The latter procedure was shown to be the method of choice. The reaction of these pentacarbonyl derivatives with CH3NH2 to form dr-[Mn(C0)4(L)C(0)NEICH3] is discussed in relation to other nucleophilic reactions at the carbonyl carbon atom. Displacement of CO ligands from the Mn(CO)s(CH3CN)+ species in solution by pyridine, phosphines, and CH3CN is also reported. In some of these multisubstituted species, exchange of the bound CH3CN ligands was observed. The CO stretching force constants were calculated for all the cationic species prepared. In the pentacarbonylmanganese phosphine derivatives the axial CO force constant, k\, was quite similar to the equatorial CO force constant, ki. This result is discussed in terms of a direct donation of phosphorus electrons into the orbitals of the equatorial CO ligands.
Dicyclopentadienylberyllium reacts with dimethylberyllium or beryllium halides in the absence of solvent to form mixed C5H5BeX complexes. The products are stable toward disproportionation and monomeric in solution and vapor phases. NMR, IR, and mass spectral data are presented. The bonding interaction between beryllium and the cyclopentadienyl ring is discussed.The preparation and characterization of mixed alkyl (RMR') and alkylmetal halides of the group 2 metals have received much attention in the literature. Redistribution reactions between dialkyl and diaryl compounds of mercury2,3 and magnesium4 have been investigated. The mercury alkyls
Infrared and Raman spectra are reported for liquid and solid C5H5BeCl, C5H5BeBH4, and C5H5BeBD4 and vibrational assignments of most of the C5H5, BeX, and skeletal modes are made. Conclusive evidence for a double hydrogen bridge configuration is found for C5H5BeBH4 and, in contrast to Be(BH4)2, this structure is unchanged in going from gas to liquid to solid. The C5H5 frequencies are in close accord with those of (C5H5)2Fe while the vibrations of the BeBH4 group are analogous to those reported earlier for the +BeBH4 ion in solid Be(BH4)2. Observation of several transitions for the skeletal torsional motion of C5H5BeBH4 implies that free internal rotation about the symmetry axis does not occur and calculations yield a value of 500 cm−1 for the tenfold torsional barrier. Raman polarization data are consistent with a low energy orientation which places the BeH2bB bridging plane and a Cs molecular symmetry plane in coincidence.
[(CH3)2AIOCH3]3 has been studied by gas phase electron diffraction. The mainmolecular parameters are R(A1C) = 1.957(3) Å, R(A10) = 1.861(3) 8, R(0C)= 1.436(3) Å,
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