Reactions of [R2P(E)]2NH (R = Ph or Pri, E = S or Se) with [Ru3(CO)12]: crystal structures of [Ru4(µ4-Se)2(µ -CO)(CO)8{(Ph2P)2NH-P, P′}], [Ru4(µ4-S)2(µ- CO)(CO)8{(Pri2P)2NH- P,P′}] and [Ru3(µ3-S)2(CO)7 {(Ph2P)2NH-P,P ′}]

Abstract

Oxidative addition of the chalcogenides [R ₂ P(E)] ₂ NH (R = Ph or Pr ⁱ , E = S or Se) to the metal carbonyl [Ru ₃ (CO) ₁₂ ] in the presence of Me ₃ NO (ca. 1∶1∶1 ratio) in toluene gave, after chromatographic separation (preparative TLC), new substituted tri- and tetra-nuclear capped sulfido (or selenido) ruthenium carbonyl complexes with (Ph ₂ P) ₂ NH or (Pr ⁱ ₂ P) ₂ NH ligands. All compounds have been characterised by a combination of multinuclear NMR [ ³¹ P-{ ¹ H} and ¹ H], IR spectroscopy and elemental analysis. Furthermore the solid-state structures of three representative examples, namely [Ru ₄ (µ ₄ -Se) ₂ (µ- CO)(CO) ₈ {(Ph ₂ P) ₂ NH-P, P′}], [Ru ₄ (µ ₄ -S) ₂ (µ- CO)(CO) ₈ {(Pr ⁱ ₂ P) ₂ NH- P,P′}] and [Ru ₃ (µ ₃ -S) ₂ (CO) ₇ {(Ph ₂ P) ₂ NH-P,P′ }] have been determined by single-crystal X-ray diffraction. In all these cases the integrity of the [R ₂ P(E)] ₂ NH ligand, under the experimental conditions employed, is not retained.