Reactions of [R2P(E)](2)NH (R=Ph or Pr-i, E=S or Se) with [Ru-3(CO)(12)]: crystal structures of [Ru-4(mu(4)-Se)(2)(mu-CO)(CO)(8)-{(Ph2P)(2)NH-P,P'}], [Ru-4(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 separation (preparative TLC), new substituted tri- and tetra-nuclear capped sulfide (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 three representative examples, namely [Ru-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 determined by single-crystal X-ray diffraction. In all these cases the integrity of the [R2P(E)](2)NH ligand, under the experimental conditions employed, is not retained.