CHEMISTRY OF POLYFUNCTIONAL MOLECULES, .115. REDUCTIVE CLEAVAGE OF (PH2P)2NH AND STABILIZING OF THE CLEAVAGE PRODUCTS IN A MONO-RADICALIC DICOBALT(1/2+) AND 2 DICOBALT(1+) CARBONYL-COMPLEXES - CRYSTAL-STRUCTURES OF THE 3 NEW COMPLEXES

[Co2(mu-CO)2(CO)4(mu-dppa)] [5; dppa = (Ph2P)2NH] reacts with dppa (1) in toluene at 85-degrees-C within 15 minutes primary to give [Co2(CO)4(mu-dppa)2] (6). After about one hour a reductive P-N bond cleavage of the coordinated dppa in 6 takes place, accompanied by hydrogen transfer, yielding [(Co1+)2(mu-CO)(CO)4(dppa-)2] (7), the paramagnetic dinuclear complex [(Co1/2+)2(mu-PPh2-)(CO)2(mu-dppa)2] (8), and [(Co1+)2(mu-CO)(CO)3(mu-PPh2-)(mu-dppa-)PPh2NH2] (9). The three new compounds 7-9 have been characterized by X-ray analyses, H-1, C-13{H-1}-NMR, IR, ESR spectroscopy, and magnetic measurements.