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Thermally induced rearrangement of. cap alpha. -zirconocenyl thioethers: carbon-carbon bond formation via a transition-metal hydroxymethyl or metalloxirane analog

Journal Article · · Organometallics; (United States)
DOI:https://doi.org/10.1021/om00091a002· OSTI ID:7247288
; ;
The thermal rearrangement of ..cap alpha..-zirconocenyl thioethers (eta/sup 5/-C/sub 5/H/sub 5/)/sub 2/Zr(Ar)(CH(SC/sub 6/H/sub 5/)(Si(CH/sub 3/)/sub 3/)) (Ar = C/sub 6/H/sub 5/, rho-C/sub 6/H/sub 4/CH/sub 3/, rho-C/sub 6/H/sub 4/OCH/sub 3/, rho-C/sub 6/H/sub 4/Cl) and (eta/sup 5/-C/sub 5/H/sub 5/)/sub 2/ZrC/sub 6/H/sub 5/(CH(SCH/sub 33/)(Si(CH/sub 3/)/sub 3/)) in toluene solution follows clean first-order kinetics to produce (eta/sup 5/-C/sub 5/H/sub 5/)/sub 2/Zr(SC/sub 6/H/sub 5/)(CH(Ar)(Si(CH/sub 3/)/sub 3/)) and (eta/sup 5/-C/sub 5/H/sub 5/)/sub 2/Zr(SCH/sub 3/)(CH(C/sub 6/H/sub 5/)(Si(CH/sub 3/)/sub 3/)). Labeling studies using (eta/sup 5/-C/sub 5/H/sub 5/)/sub 2/Zr(rho-C/sub 6/H/sub 4/CH/sub 3/)(CH(SC/sub 6/H/sub 5/)(Si(CH/sub 3/)/sub 3/)) and (eta/sup 5/-C/sub 5/H/sub 5/)/sub 2/ZrC/sub 6/H/sub 5/(CD(SC/sub 6/H/sub 5/)(Si(CH/sub 3/)/sub 3/)) show this rearrangement to be intramolecular. Activation parameters for the rearrangement of (eta/sup 5/-C/sub 5/H/sub 5/)/sub 2/ZrC/sub 6/H/sub 5/(CH(SC/sub 6/H/sub 5/)(Si(CH/sub 3/)/sub 3/)) were found to be ..delta..H++ = 20.30 (43) kcal,mol and ..delta..S++ = -19.0 (2) eu. It is proposed that this rearrangement proceeds by intramolecular nucleophilic attack (migration) of the aryl group to the methylene carbon with commensurate breaking of the C-S bond. A Hammett plot of log (k/sub obsd/) for the rearrangement of (eta/sup 5/-C/sub 5/H/sub 5/)/sub 2/Zr(Ar)(CH(SC/sub 6/H/sub 5/)(Si(CH/sub 3/)/sub 3/)) versus sigma/sub rho/ produces a straight line (rho = 2.22 (9), supporting this mechanism.
Research Organization:
West Virginia Univ., Morgantown (USA)
OSTI ID:
7247288
Journal Information:
Organometallics; (United States), Journal Name: Organometallics; (United States) Vol. 7:1; ISSN ORGND
Country of Publication:
United States
Language:
English

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Related Subjects

01 COAL, LIGNITE, AND PEAT
010408 -- Coal
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& Peat-- C1 Processes-- (1987-)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACTIVATION ENERGY
ALKYLATED AROMATICS
AROMATICS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DEUTERIUM
ENERGY
EXPERIMENTAL DATA
HEATING
HYDROCARBONS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
KINETICS
LABELLING
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
REACTION KINETICS
STABLE ISOTOPES
SULFIDES
SULFUR COMPOUNDS
THERMODYNAMICS
TOLUENE
TRANSITION ELEMENT COMPOUNDS
ZIRCONIUM COMPOUNDS