Nitrosyl complexes of rhenium. 2. Neutral and cationic monohydride complexes of rhenium(I) resulting from the reaction of ReH/sub 2/(NO)(PPh/sub 3/)/sub 3/ with perchloric acid
The rhenium dihydride complex ReH/sub 2/(NO)(PPh/sub 3/)/sub 3/ reacts with HClO/sub 4/ in the presence of CO with the cleavage of only one hydride ligand. Control of the degree of acidity and the solvent system leads to isolation of compounds such as ReH(OR)(CO)(NO)(PPh/sub 3/)/sub 2/ (R = Me, Et) and (ReH(CO)(NO)(PPh/sub 3/)/sub 3/)ClO/sub 4/. The alkoxide complexes are protonated by HClO/sub 4/ to yield alcohol complexes ReH(ROH.OClO/sub 3/)(CO)(NO)(PPh/sub 3/)/sub 2/. Heating ReH(MeOH.OClO/sub 3/)(CO)(NO)(PPh/sub 3/)/sub 2/ in methanol results in the formal 1,2-elimination of dihydrogen with formation of Re(OMe)(OClO/sub 3/)(CO)(NO)(PPh/sub 3/)/sub 2/. A similar elimination reaction occurs when the alcohol complexes are reacted with halide ions to give ReX(OR)(CO)(NO(PPh/sub 3/)/sub 2/ (X = Cl, Br, I). Reacting the alcohol complexes with base or NaBH/sub 4/ however, regenerates ReH(OR)(CO)(NO)(PPh/sub 3/)/sub 2/. The perchlorate complex, Re(OMe)(OClO/sub 3/)(CO)(NO)(PPh/sub 3/)/sub 2/ reacts with NaBH/sub 4/ to give ReH/sub 2/(CO)(NO)(PPh/sub 3/)/sub 2/ via a borohydride complex. The chloro-alkoxy complexes ReCl(OR)(CO)(NO)(PPh/sub 3/)/sub 2/ also react with HClO/sub 4/ to give alcohol complexes. All structural assignments have been made on the basis of elemental analysis, infrared spectroscopy, /sup 1/H NMR spectroscopy, and deuteration studies. 14 references, 2 figures, 2 tables.
- Research Organization:
- Dalhousie Univ., Halifax, Nova Scotia
- OSTI ID:
- 5815932
- Journal Information:
- Inorg. Chem.; (United States), Vol. 24:23
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALCOHOLS
CHEMICAL REACTIONS
HALIDES
HYDRIDES
STRUCTURAL CHEMICAL ANALYSIS
PERCHLORIC ACID
RHENIUM COMPLEXES
CARBON MONOXIDE
CHEMICAL REACTION YIELD
EXPERIMENTAL DATA
HYDROGEN
INFRARED SPECTRA
ISOTOPE EFFECTS
LIGANDS
NMR SPECTRA
PH VALUE
CARBON COMPOUNDS
CARBON OXIDES
CHALCOGENIDES
COMPLEXES
DATA
ELEMENTS
HALOGEN COMPOUNDS
HYDROGEN COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
INORGANIC ACIDS
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
SPECTRA
TRANSITION ELEMENT COMPLEXES
YIELDS
400201* - Chemical & Physicochemical Properties