MULTIPLE BONDS BETWEEN TRANSITION-METALS AND MAIN-GROUP ELEMENTS .163. NITROGEN-DONOR ADDUCTS OF ORGANORHENIUM(VII) OXIDES - STRUCTURAL ANDCATALYTIC ASPECTS

N-base adducts of methyltrioxorhenium(VII) (1), characterized by their structural and spectroscopic data, are compared with respect to die i nfluence of the pK(b) values of the N-bases. The crystal structure of one of these derivatives, namely the adduct of Troger's base yl-6H,12H -5,11-methanodibenzo[b,f]-[1,5]diazocine) with compound 1 (2a) is repo rted. The cell constants are a:; follows: a = 1281.6(2)pm, b = 833.9(1 )pm, c = 1705.5(2) pm, beta = 106.09(1)degrees, V = 1751.2(4) x 10(6) pm(3). Derivative 2a exhibits the longest Re(VII)-N bond distance know n to date. Furthermore, 2a is the first adduct of Troger's base whose structure has been examined by X-ray crystallography. Epoxidation and sulfoxidation catalysis with N-base adducts of 1 is described, the inf luence of the Re-N bond strength on the catalytic processes is discuss ed.