Organorhenium imido complexes: Synthese, structure, and reactivity
- Universitaet Muenchen (Germany, F.R.)
Imido complexes of heptavalent rhenium have been synthesized by three different routes: (i) aminolysis of the half-sandwich complex ({eta}{sup 5}-C{sub 5}Me{sub 5})ReCl{sub 4} (1) (Me = CH{sub 3}) with primary amines gives the imidoderivatives ({eta}{sup 5}-C{sub 5}Me{sub 5})Re(N{sup t}Bu)Cl{sub 2} (2a, {sup t}Bu = tert-butyl) and ({eta}{sup 5}-C{sub 5}Me{sub 5})Re(NCH{sub 3})Cl{sub 2} (2b). The rhenium-nitrogen distance in compound 2a (1.709 (3) {angstrom}) corresponds to a triple bond (single-crystal X-ray diffraction), while the analogous oxo congener ({eta}{sup 5}-C{sub 5}Me{sub 5})ReOCl{sub 2} has relatively little rhenium-oxygen triple-bond character. (ii) Sequential deoxygenation of methyltrioxorhenium(VII) (6) via decarboxylation upon treatment with 2,6-diisopropylphenyl isocyanate yields mono- and dinuclear methylrhenium(VII) imido complexes in good yields; imido bridging occurs when the mononuclear compounds of types CH{sub 3}ReO(NR){sub 2} and CH{sub 3}Re(NR){sub 3} are dissolved in polar solvents such as typically 1,2-dimethoxyethane. (iii) Nucleophilic substitution of Me{sub 3}SiO-Re(N{sup t}Bu){sub 3} by organolithium or Grignard reagents was used to synthesize the new methyl-, allyl-, ethyl-, and phenylalkynyl derivatives R{prime}-Re(N{sup t}Bu){sub 3} (R{prime} = CH{sub 3}, C{sub 3}H{sub 5}, C{sub 2}H{sub 5}, C{sub 6}H{sub 5}C{triple bond}C).
- OSTI ID:
- 7108165
- Journal Information:
- Organometallics; (USA), Journal Name: Organometallics; (USA) Vol. 9:2; ISSN 0276-7333; ISSN ORGND
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
CALCULATION METHODS
COMPLEXES
CRYSTAL STRUCTURE
DATA
DATA ANALYSIS
EXPERIMENTAL DATA
INFORMATION
LIGANDS
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
RHENIUM COMPLEXES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES