Synthesis and reactivity of air-stable (LRe(NO)(CO)(CH/sub 3/))/sup +/ (L = 1,4,7-triazacyclononane). Kinetics and mechanism of its reactions with HX (X = Cl, Br, NO/sub 3/). Formation of ((LRe(NO)(CO))/sub 2/(. mu. -CH/sub 2/OCH/sub 2/))I/sub 2/ containing a bridging 2-oxapropane-1,3-diide
The reaction of (LRe(NO)(CO)/sub 2/)BF/sub 4/ in aqueous solution with NaBH/sub 4/ affords red, racemic (LRe(NO)(CO)(CH/sub 3/))BF/sub 4/ (1), which has been resolved into its enantiomerically pure form as the (1S)-3-bromocamphorsulfonate salt (L = 1,4,7-triazacyclononane, C/sub 6/H/sub 15/N/sub 3/). 1 reacts in aqueous solution with HX (X = F, Cl, Br, I) to yield the compounds (LRe(NO)(CO)X)/sup +/ and methane. The kinetics of the reactions have been measured. A third-order rate law, -d(1)/dt = k(1)(X)(H/sup +/), has been established. The formal substitution reaction proceeds with retention of configuration at the Re center. A mechanism is proposed that involves the acid-catalyzed cleavage of an Re-N/sub amine/ bond, followed by nucleophilic attack of the nucleophile X/sup -/ at the 16e fragment with concomitant expulsion of CH/sub 3//sup -/ (which is immediately protonated) and rapid re-formation of the Re-N/sub amine/ bond. 1 reacts with I/sub 2/, forming (LRe(NO)(CO)(CH/sub 2/I))/sup +/, which dimerizes in aqueous solution generating ((LRe(NO)(CO))/sub 2/(..mu..-CH/sub 2/OCH/sub 2/))I/sub 2/, which contains the novel bridging group 2-oxapropane-1,3-diide. (LRe(NO)(CO)(O/sub 2/CCF/sub 3/))/sup +/ (2) has been prepared from 1 in F/sub 3/CCO/sub 2/H. 2 reacts with bromine to form the paramagnetic Re(II) complex (LRe(NO)(CO)Br)/sup 2 +/, which is reduced by BH/sub 4//sup -/ to yield (LRe(NO)(CH/sub 3/)Br); oxidation of the latter species with Br/sub 2/ yields (LRe(NO)Br/sub 2/)/sup +/, which is reduced by zinc amalgam to (LRe(NO)Br/sub 2/). Spectroscopic (IR, /sup 1/H NMR, /sup 13/C NMR) and magnetic properties of all new compounds are reported as well as their electrochemical behavior. 36 references, 6 figures, 2 tables.
- Research Organization:
- Ruhr-Universitaet, Bochum (West Germany)
- OSTI ID:
- 6260215
- Journal Information:
- Inorg. Chem.; (United States), Vol. 27:21
- Country of Publication:
- United States
- Language:
- English
Similar Records
Metal control of the reaction site in reactions of[{({eta}{sup 5}-C{sub 5}H{sub 3}){sub 2}(SiMe{sub 2}){sub 2}}M{sub 2}(CO){sub 4}({mu}-H)]{sup+} (M= Fe, Ru, Os) with nucleophilic amines.
Preparation and characterization of binuclear complexes of molybdenum(III) and molybdenum(V) via oxidative decarbonylation. Reactions of LMo(CO)/sub 3/ (L = 1,5,9-triazacyclododecane) and crystal structure of anti-(L/sub 2/Mo/sub 2/O/sub 4/)(ClO/sub 4/)/sub 2/ x 2H/sub 2/O
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKANES
SYNTHESIS
BROMINE COMPOUNDS
CARBONYLS
CHLORINE COMPOUNDS
HETEROCYCLIC COMPOUNDS
NITROGEN COMPOUNDS
RHENIUM COMPOUNDS
CARBON 13
CHEMICAL REACTIONS
ELECTROCHEMISTRY
EXPERIMENTAL DATA
MAGNETIC PROPERTIES
NMR SPECTRA
PROTONS
BARYONS
CARBON ISOTOPES
CHEMISTRY
DATA
ELEMENTARY PARTICLES
EVEN-ODD NUCLEI
FERMIONS
HADRONS
HALOGEN COMPOUNDS
HYDROCARBONS
INFORMATION
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUCLEONS
NUMERICAL DATA
ORGANIC COMPOUNDS
PHYSICAL PROPERTIES
REFRACTORY METAL COMPOUNDS
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPOUNDS
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation