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

Journal Article · Tue Nov 05 23:00:00 EST 1985 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00217a041· OSTI ID:5815932

Grundy, K R; Robertson, K N

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), Journal Name: Inorg. Chem.; (United States) Vol. 24:23; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALCOHOLS
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMPLEXES
DATA
ELEMENTS
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
HYDRIDES
HYDROGEN
HYDROGEN COMPOUNDS
HYDROXY COMPOUNDS
INFORMATION
INFRARED SPECTRA
INORGANIC ACIDS
ISOTOPE EFFECTS
LIGANDS
NMR SPECTRA
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PERCHLORIC ACID
PH VALUE
RHENIUM COMPLEXES
SPECTRA
STRUCTURAL CHEMICAL ANALYSIS
TRANSITION ELEMENT COMPLEXES
YIELDS