Comparative reactivities of two isoelectronic transition-metal hydrides with transition-metal carbonyls and alkyls

Journal Article · Wed Jul 29 00:00:00 EDT 1981 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00405a022· OSTI ID:6065819

Jones, W D; Huggins, J M; Bergman, R G

The two isoelectronic hydrides PPN/sup +/CpV(CO)/sub 3/H/sup -/ (1) and -CpMo(CO)/sub 3/H (2) react with a variety of metal carbonyls and alkyls. Treatment of Fe(CO)/sub 5/, Cr(CO)/sub 6/, (CH/sub 3/C/sub 5/H/sub 4/)V(CO)/sub 4/, CH/sub 3/Re(CO)/sub 5/, and (CH/sub 3/CO)Re(CO)/sub 5/ with 1 produces HFe(CO)/sub 4//sup -/, HCr(CO)/sub 5//sup -/, (CH/sub 3/C/sub 5/H/sub 4/)V(CO)/sub 3/H/sup -/, (H)(CH/sub 3/)Re(CO)/sub 4//sup -/, and (H)(CH/sub 3/CO)Re(CO)/sub 4//sup -/, respectively, and CpV(CO)/sub 4/ (3). l also catalyzes ligand substitution reactions in 3 and CpFe(CO)(PPh/sub 3/)(COCH/sub 3/). In comparison 2 reacts only with CH/sub 3/Mn(CO)/sub 5/ and CpMo(CO)/sub 3/R(R = CH/sub 3/, C/sub 2/H/sub 5/, CH/sub 2/C/sub 6/H/sub 5/) producing aldehydes and the dimers (CpMo(CO)/sub 3/)/sub 2/ (4a) and (CpMo(CO)/sub 2/)/sub 2/ (5a). Reaction of 2 with ethylene produces ethane and diethyl ketone. l is proposed to react by an electron-transfer mechanism, whereas 2 is proposed to react by hydrogen transfer to a vacant coordination site. The relationship of the molybdenum hydride/alkyl reaction to the final step in hydroformylation (oxo process) is discussed.

• Research Organization: Univ. of California, Berkeley, CA (United States)
• OSTI ID: 6065819
• Journal Information: J. Am. Chem. Soc.; (United States), Vol. 103:15
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
MOLYBDENUM COMPLEXES
CHEMICAL REACTIONS
VANADIUM COMPLEXES
CARBONYLS
CHROMIUM COMPLEXES
CYCLOPENTADIENE
HYDRIDES
IRON COMPLEXES
RHENIUM COMPLEXES
ALKENES
COMPLEXES
CYCLOALKENES
DIENES
HYDROCARBONS
HYDROGEN COMPOUNDS
ORGANIC COMPOUNDS
POLYENES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties