Multiple bonds between main-group elements and transition metals. 77. Condensation reactions of methyltrioxorhenium(VII) with catechols and aromatic thiols

Abstract

The title compound methyltrioxorhenium (VII) reacts with catechols to yield complexes of the formula CH 3 Re(O) 2 (1,2-O 2 C 6 R 4 ) ( ) that are fully characterized as pyridine adducts 3. Conducting these reactions in the presence of nucleophiles, e.g; halides, gives the hexacoordinate anions [CH 3 Re(O) 2 (1,2-O 2 C 6 R 4 )(X)] - (X=Cl,Br,I). The rhenium (V) species «CH 3 ReO 2 », prepared in situ from 1 by reduction with (polymer bound) triphenylphosphane, reacts with phenanthrenequinone in the presence of pyridine to give the neutral hexacoordinate complex CH 3 Re(O) 2 (9,10,O 2 C 14 H 8 )(NC 5 H 5 ) (5). Reaction of 1 with thiophenol gives initially the rhenium (VII) complex CH 3 ReO(SC 6 H 5 ) 4 (6), which upon heating undergoes intramolecular elimination of diphenyl disulfide, C 6 H 5 SSC 6 H 5 , to give the dinuclear rhenium (V) complex [CH 3 ReO(μ-SC 6 H 5 )(SC 6 H 5 )] 2 (7;X-ray diffraction study). Condensation of 1 with benzene-1,2-dithiol gives the rhenium (VII) complex CH 3 ReO(1,2-S 2 C 6 H 4 ) 2 (8)