REACTIONS OF [R2P(E)](2)NH (R=PH OR PR-I, E=S OR SE) WITH [RU-3(CO)(12)] - CRYSTAL-STRUCTURES OF -4(MU(4)-SE)(2)(MU-CO)(CO)(8)-((PH2P)(2)NH-P,P')], (MU(4)-S)(2)(MU-CO)(CO)(8)((PR(I)(2)P)(2)NH-P,P')] AND [RU-3(MU(3)-S)(2)(CO)(7)((PH2P)(2)NH-P,P')]

Oxidative addition of the chalcogenides [R2P(E)](2)NH (R = Ph or Pr-i, E = S or Se) to the metal carbonyl [Ru-3(CO)(12)] in the presence of Me3NO (ca. 1:1:1 ratio) in toluene gave, after chromatographic separat ion (preparative TLC), new substituted tri- and tetra-nuclear capped s ulfide (or selenido) ruthenium carbonyl complexes with (Ph2P)(2)NH or ((Pr2P)-P-i)(2)NH ligands. All compounds have been characterised by a combination of multinuclear NMR [P-31-{H-1} and H-1], IR spectroscopy and elemental analysis. Furthermore the solid-state structures of thre e representative examples, namely u-4(mu(4)-Se)(2)(mu-Co)(Co)(8){(Ph2P )(2)NH-P,P'}], [Ru-4(mu(4)-S)(2)-(mu-CO)(CO)(8) {((Pr2P)-P-i)(2)NH-P, P'}] and [Ru-3(mu(3)-S)(2)(CO)(7){(Ph2P)(2)NH-P,P'}] have been determi ned by single-crystal X-ray diffraction. In all these cases the integr ity of the [R2P(E)](2)NH ligand, under the experimental conditions emp loyed, is not retained.