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Title: Characterization of the organometallic Lewis acid (/eta//sup 5/-C/sub 5/H/sub 5/)(CO)Fe(OR/sub 2/)(/eta//sup 2/-CH/sub 2/ = CHCH/sub 3/)/sup +/BF/sub 4//sup /minus//

Journal Article · · Organometallics; (United States)
DOI:https://doi.org/10.1021/om00098a014· OSTI ID:5762557
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Protonation of the /eta//sup 3/-allyl complex Cp(CO)Fe(CH/sub 2/CHCH/sub 2/) (10) with HBF/sub 4//center dot/OEt/sub 2/ or HBF/sub 4//center dot/OMe/sub 2/ in CH/sub 2/Cl/sub 2/ (/minus/80/degree/C) affords an extremely reactive organometallic Lewis acid precursor, which degrades above /minus/65/degree/C. The structure assigned to this Lewis acid, on the basis of its /sup 11/B and /sup 19/F NMR spectral measurements and of its chemical reactivity, is Cp(CO)Fe(OR/sub 2/)(CH/sub 2//emdash/CHCH/sub 3/)/sup +/BF/sub 4//sup /minus// (8). Similar NMR measurements are also reported for appropriate model compounds containing coordinated fluoroborate (e.g., Cp(CO)/sub 2/FeFBF/sub 3/ and Cp(CO)/sub 3/MoFBF/sub 3/) or ionic BF/sub 4//sup /minus// e.g., Cp(CO)/sub 2/Fe(THF)/sup +/FB/sub 4//sup /minus//. Some potential ligands (e.g., THF) deprotonate 8 back to starting 10, whereas others (e.g., acetonitrile) readily convert 8 into examples of disubstituted complexes, Cp(CO)Fe(L/sub 1/)(L/sub 2/)/sup +/BF/sub 4//sup /minus//. Excess P(OPh)/sub 3/, for example, converts 8 first to the /eta//sup 2/-propene derivative Cp(CO)Fe(CH/sub 2//emdash/CHCH/sub 3/)P(OPh)/sub 3//sup +/BF/sub 4//sup /minus// (13) and then in refluxing CH/sub 2/Cl/sub 2/ to Cp(CO)Fe(P(OPh)/sub 3/)/sub 2//sup +/BF/sub 4//sup /minus// (14). Reactions between 8 and the acetyl complexes Cp(CO)(L)FeCOCH/sub 3/ (L = CO, PPh/sub 3/) give the bimetallic /mu/-(/eta//sup 1/-C,O)-acetyl compounds Cp(CO)(L)Fe-C(CH/sub 3/)O-Fe(CO)/sub 2/Cp/sup +/BF/sub 4//sup /minus// (15) in low yields, with no evidence of forming /mu/-(/eta//sup 2/-C,O)-acetyl derivatives Cp(CO)Fe(CH/sub 3/CO)Fe(L)Cp/sup +/BF/sub 4//sup /minus//. The organometallic etherate complex Cp(CO)/sub 2/Fe(OMe/sub 2/)/sup +/BF/sub 4//sup /minus// (2a) results through protonolysis of Cp(CO)/sub 2/FeCH/sub 3/ with HBF/sub 4//center dot/OMe/sub 2/ between /minus/30 and /minus/78/degree/C.

Research Organization:
Rensselaer Polytechnic Institute, Troy, NY (USA)
OSTI ID:
5762557
Journal Information:
Organometallics; (United States), Vol. 7:8
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
IRON COMPLEXES
CHEMICAL REACTIONS
STRUCTURAL CHEMICAL ANALYSIS
LEWIS ACIDS
ORGANOMETALLIC COMPOUNDS
BORON 11
EXPERIMENTAL DATA
FLUORINE 19
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
BORON ISOTOPES
COMPLEXES
DATA
FLUORINE ISOTOPES
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
RESONANCE
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties