SYNTHESIS AND CRYSTAL-STRUCTURES OF OXONIUM ION COMPLEXES OF 21-CROWN-7 AND DIBENZO-30-CROWN-10

The reactions of [W(CO)(6)] with 21-crown-7 (1,4,7,10,13,16,19-heptaox acyclohenicosane) or dibenzo-30-crown-10 ,4,7,10,13,16,19,22,25,28]dec aoxacyclotriacontine) in the presence of water and HCl(g) in toluene h ave been explored. They were promoted by the use of UV radiation and f ormed liquid clathrates almost immediately. In each case, oxidation of the tungsten center from either to +2, +5 or +6 occurred. In the reac tion of 21-crown-7 with [W(CO)(6)] structural data suggest that the H5 O2+ ion is selectively co-ordinated through hydrogen bonds to the 21-c rown ether, in the tungsten(vr) complex, [H5O2+. 21-crown-7][WOCl5-] 1 , which crystallized from the liquid clathrate layer. For the reaction of dibenzo-30-crown-10 with [W(CO)(6)] initially the tungsten(II) com plex [2H(3)O(+). dibenzo-30-crown-10][W(CO)(4)Cl-3(-)](2) . 2C(6)H(5)M e 2 formed. Upon exposure of 2 to the atmosphere for cn. 30 min the tu ngsten(v) complex [2H(3)O(+). dibenzo-30-crown-10][WOCl4(H2O)(-)](2) 3 was produced. The structures of each of these complexes were establis hed by X-ray crystallography.