122383-55-5Relevant academic research and scientific papers
Monomeric rhenium (IV) phenoxides and their development from mononuclear rhenium halides with oxygen and sulfur donor ligands
Gardiner, Ian M.,Bruck, Michael A.,Wexler, Pamela A.,Wigley, David E.
, p. 3688 - 3695 (2008/10/08)
The homoleptic phenoxide complexes Re(DIPP)4 (1, DIPP = 2,6-diisopropylphenoxide) and Re(DMP)4 (2, DMP = 2,6-dimethylphenoxide) have been prepared by the reaction of ReCl4(THF)2 with Li(DIPP)·OEt2 and Li(DMP)·THF, respectively. Re(DIPP)4 crystallizes in the monoclinic space group P21/c with a = 22.657 (3) A?, b = 11.498 (2) A?, c = 18.605 (3) A?, β= 110.62 (1)°, V = 4536.2 A?3, and Z = 4 with final R = 0.035 and Rw = 0.044. While Re(DIPP)4 does not react with the internal acetylenes RC≡CR (R = Me, Et, Ph), less crowded Re(DMP)4 reacts with RC≡CR to form the adducts Re(RC≡CR)(DMP)4 (3, R = Me; 4, R = Et; 5, R = Ph). The new monomeric halides trans-ReBr4(THT)2 (6) and trans-ReCl4(THT)2 (7, THT = tetrahydrothiophene) have been prepared in high yield by refluxing K2ReX6 in concentrated HX (X = Br, Cl) and THT. Reducing ReX4(THT)2 with zinc in neat THT yields compounds of the formula mer-ReX3(THT)3 (8, X = Br; 9, X = Cl). mer-ReBr3(THT)3 crystallizes in the orthorhombic space group Pbca with a = 15.300 (2) A?, b = 14.976 (2) A?, c = 16.969 (2) A?, V = 3888.3 A?3, and Z = 8 with final R = 0.046 and Rw = 0.051. Cyclic voltammetry studies on compounds 1-9 reveal that the Re(III)-Re(IV) couple is accessible for all compounds, and it is seen to shift to more negative potentials as THT is replaced by halide followed by phenoxide.
