Synthesis and characterization of thioaldehyde hydride derivatives of permethyltantalocene. Investigations of their equilibration with thiolates and the stereochemistry of alkyl migrations from sulfur to tantalum

Journal Article · Mon Jun 01 04:00:00 EDT 1992 · Organometallics

DOI:https://doi.org/10.1021/om00042a036· OSTI ID:458731

Nelson, J E; Parkin, G; Bercaw, J E ^[1]

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1. California Institute of Technology, Pasadena, CA (United States)

The authors present the a method for preparation of permethyltantalocene thioaldehyde hydride complexes, Cp*{sub 2}Ta({eta}{sup 2}-S-CHR)H(Cp* = {eta}{sup 5}-C{sub 5}Me{sub 5}; R = H, C{sub 6}H{sub 5}, CH{sub 2}C{sub 6}H{sub 5}, CH{sub 2}CMe{sub 3}) and the X-ray crystal structure for Cp*{sub 2}Ta({eta}{sup 2}-S-CHCH{sub 2}C{sub 6}H{sub 5})H is discussed. Permethyltantalocene thioadldehyde hydride complexes are shown to be in rapid equilibrium with [Cp*{sub 2}Ta-SCH{sub 2}R]. The thermodynamically favored tautomer, the permethyltantalocene sulfido alkyl Cp*[{sub 2}Ta(=S)CH{sub 2}R] is formed on heating. A mechanism for the equilibration process is derived from kinetic data and stereochemistry of the alkyl migration is quantified. 38 refs., 2 figs., 1 tab.

• Sponsoring Organization: USDOE
• OSTI ID: 458731
• Journal Information: Organometallics, Journal Name: Organometallics Journal Issue: 6 Vol. 11; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
HYDROGENATION
ORGANOMETALLIC COMPOUNDS
STEREOCHEMISTRY
SULFUR COMPOUNDS
TANTALUM COMPLEXES