Nucleophilic activation of coordinated carbon monoxide. Reaction of tungsten hexacarbonyl with methoxide salts
Journal Article
·
· Inorganic Chemistry; (United States)
- San Francisco State Univ., CA (United States)
Kinetics studies of the reactions of [Na[sup +]][OCH[sub 3][minus]] and [((C[sub 6]H[sub 5])[sub 3]P)[sub 2]N[sup +]][OCH[sub 3][minus]] with W(CO)[sub 6] are reported. The preparation of acetonitrile solutions of ((C[sub 6]H[sub 5])[sub 3]P)[sub 2]NOCH[sub 3], a convenient source of solubilized methoxide ion in aprotic media, is described. Second-order rate constants (730 [plus minus] 130 M[sup [minus]1] and 743 [plus minus] 61 M[sup [minus]1] s[sup [minus]1]) and equilibrium constants (3200 [plus minus] 300 M[sup [minus]1] and 1400 [plus minus] 200 M[sup [minus]1]) for the formation of the methoxycarbonyl complexes [M[sup +]][W(CO)[sub 5]CO[sub 2]CH[sub 3][minus]] (M[sup +] = Na[sup +] and ((C[sub 6]H[sub 5])[sub 3]P)[sub 2]N[sup +], respectively) at 25[degrees]C are several orders of magnitude lower than those reported for the formation of group VIII methoxycarbonyl complexes. Addition of trace quantities of water to THF/CH[sub 3]OH solutions of [Na[sup +]][W(CO)[sub 5]CO[sub 2]CH[sub 3][minus]] surprisingly resulted in the formation of W(CO)[sub 6] and not the expected metal hydride HW(CO)[sub 5][minus]. These observations are consistent with the previously reported variation in catalytic activity of group VI and VIII metal carbonyl compounds for the water gas shift reaction.
- OSTI ID:
- 5866401
- Journal Information:
- Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 32:12; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKOXIDES
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL ACTIVATION
CHEMICAL REACTION KINETICS
COMPLEXES
EQUILIBRIUM
FLUIDS
FUEL GAS
FUELS
GAS FUELS
GASES
INTERMEDIATE BTU GAS
KINETICS
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REACTION KINETICS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES
WATER GAS
400201* -- Chemical & Physicochemical Properties
ALKOXIDES
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL ACTIVATION
CHEMICAL REACTION KINETICS
COMPLEXES
EQUILIBRIUM
FLUIDS
FUEL GAS
FUELS
GAS FUELS
GASES
INTERMEDIATE BTU GAS
KINETICS
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REACTION KINETICS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES
WATER GAS