Chemie Polyfunktioneller Moleküle: CII. Metallpentacarbonyl- und Cobaltnitrosylcarbonyl-Komplexe eines Diphenylphosphin-substituierten Cyclophosphamids. Röntgenstrukturanalyse des Bis(dicarbonylnitrosylcobalt)-Derivats

Abstract

Treatment of rac-(Ph 2PCH 2CH 2) 2N P(O)NH(CH 2) 3O ( 2) with M(CO) 5THF (M = Cr, Mo, W) gives the bimetallic complexes rac-[(OC) 5MPPh 2CH 2CH 2] 2N P(O)NH(CH 2) 3O ( 3a–c). The reaction of 2 with Co(CO) 3NO yields the analogous cobalt complex rac-[(OC) 2Co(NO)PPh 2CH 2CH 2] 2N P(O)NH(CH 2) 3O ( 4). In boiling toluene 4 reacts, under elimination of CO, to give the bicyclic compound rac-(OC)(ON)Co(PPh 2CH 2CH 2) 2N P(O)NH(CH 2) 3O ( 5). The complexes have been characterized by 1H, 31P and 13C NMR, IR, Raman and mass spectroscopy as far as possible. The crystal structure of 4 has been determined by X-ray diffraction studies. The crystals are monoclinic, space group P2 1/ c with a 1296.6(4), b 1745.2(5), c 1974.2(8) pm, β 105.73(3)° and Z = 4. The molecule consists of an organophosphorus six-membered ring. Each dicarbonylnitrosylcobalt group is coordinated by the diphenylphosphine group of both of the sidechains. In the cystal each R-enantiomer is connected with its S-enantiomer by hydrogen bonds.