144812-17-9Relevant academic research and scientific papers
Synthesis, structure, and exchange reactions of rhenium alkoxide and aryloxide complexes. Evidence for both proton and hydrogen atom transfer in the exchange transition state
Simpson, Robert D.,Bergman, Robert G.
, p. 781 - 796 (2008/10/08)
A series of rhenium(I) aryloxide and alkoxide complexes have been prepared. The aryloxide complexes may be prepared by treatment of the methyl complex (CO)3(PPh3)2ReCH3 (1) with p-cresol, affording (CO)3(PPh3)2ReOC6H 4CH3 (3a). The PPh3 ligands may be displaced by a number of other ligands (PMe3, 1,2-(dimethylarsino)benzene (diars), or t-BuNC), providing a route to substituted cresolate complexes. Alkoxide complexes of the type (CO)3(L)2ReOR (R = CH3 (6), CH2CH3 (7), CH(CH3)3 (8); L, L2 = PMe3, diars, depe, or (S,S)-bdpp) may be prepared by treatment of the triflate complexes (CO)3(L)2ReOSO2CF3 with the sodium salt of the appropriate alcohol. These alkoxide complexes are quite stable and do not decompose by β-hydride elimination. The coordinated alkoxide ligands exchange rapidly with added alcohols in solution, while the exchange of aryloxide ligands with added phenols is much slower. The alkoxide complexes may be converted into the aryloxide complexes by addition of the desired phenol and heating to 44°C. This reaction proceeds via the intermediacy of a hydrogen-bonded adduct formed by coordination of the phenol O-H proton to the alkoxide oxygen atom. The hydrogen bonds are quite strong, and the adducts may be isolated if desired. One of the hydrogen-bonded adducts of 7e and p-cresol, (CO)3(depe)ReOCH2CH3?HOC 6H4CH3, has been structurally characterized. The O-O distance is 2.532(5) A?, a value commonly observed for strong hydrogen bonds. The rates of conversion of a series of these complexes (CO)3(diars)ReOCH3?HOC6H4X (6b?HOC6H4X) to (CO)3(diars)ReOC6H4X (3b) and methanol were studied. The rate of this reaction was found to be cleanly first order in the hydrogen-bonded complex 6b?HOC6H4X and was unaffected by the addition of excess phenol and added bases. The rate was found to increase when the substituent X either lowers the O-H bond dissociation energy or increases the acidity of the phenol, indicating that the transition state for this reaction can have either proton or hydrogen atom transfer character.
Comparison of the reactivity of (CO)3L2ReOR, (CO)3L2ReOAr, and (CO)3L2ReNHAr with CO2 and other electrophiles
Simpson, Robert D.,Bergman, Robert G.
, p. 4306 - 4315 (2008/10/08)
The reactivity of a series of low-valent Re alkoxides, aryloxides, and arylamides with CO2, CS2, and other electrophiles has been investigated. The methoxide complexes fac-(CO)3(L2)ReOCH3 (2a, L = PMe3; 2b, L2 = 1,2-(AsMe2)2C6H4 (diars)) react with activated organic carbonyl compounds such as acid chlorides, anhydrides, and activated esters to give products resulting from cleavage of the Re-OCH3 bond. The methoxide complexes react rapidly with CO2 and CS2 to give the expected insertion products fac-(CO)3(L2)ReX(CX)OCH3 (8, X = O; 9, X = S). The analogous aryloxides 1 do not react with CO2 and only the PMe3-substituted system reacts with CS2. In the latter transformation fac,cis-(CO)3-(PMe3)2ReOC6H 4CH3 leads to the isomerized product mer,trans-(CO)3(PMe3)2ReS(CS)OC 6H4CH3. The arylamide fac-(CO)3(depe)ReNHC6H5 (3c) reacts with CO2 to give the metallaurethane 10c. The metallacarbonates 8 were found to be quite reactive. They readily deinsert CO2 to reform the methoxide complexes. Hydrolysis of 8b leads to a bridging carbonate complex (CO)3(diars)Re-(μ-CO3)-Re(diars)(CO)3, whose structure has been determined by an X-ray diffraction study. Kinetic studies on the formation of 9b suggest that the reaction of 2b with CX2 is a simple bimolecular process.
