Tetranuclear ruthenium clusters containing a pseudo-octahedral Ru₄S₂framework and diaminocarbene ligands

Novel hexanuclear ruthenium clusters with unusual metal framework geometries: ‘boat’ and ‘sofa’ configurations of the Ru6core

“…Even weaker is the stabilizing effect of the bridging nitrogen atom of the diaminocarbene ligand, accounting for the bond length of 3.231(3) A. The elongation of the distances Ru( 1)-Ru (5) and Ru(2)-Ru (4) observed in 1 can be interpreted as a bond order of 0.5, which in turn satisfies the effective atomic number rule for 1.…”

“…Four of these atoms form an approximately planar trapezoid (planar to within kO.03 A). The distances Ru( 1)-Ru (5) and Ru(2)-Ru( 4) are unusually long [3.231(3) and 3.081(3) A]; Ru(lFRu(2) [2.917(3) A] and Ru(4)-Ru(5) [2.930(3) A] are also longer than those found in [Ru~(CO),,].~…”

“…As in the trinuclear cluster 3, the sulfur atom of the thioureato ligand is bridging and the nitrogen atom is co-ordinated terminally. The distances Ru(2)- The second triangular substructure composed of Ru(l), Ru (5) and Ru(6) in compound 1 is bridged, on the side opposite to atom S(1) by a p3-q2-bound N,N'-diethyldiaminocarbene ligand. The N atom bridges Ru (1) and Ru(5) [mean 2.26(2) A] while the carbene carbon atom is bound exclusively to Ru (6) [Ru( 6)-C(3), 2.10(2) A].…”

“…The distances Ru(2)- The second triangular substructure composed of Ru(l), Ru (5) and Ru(6) in compound 1 is bridged, on the side opposite to atom S(1) by a p3-q2-bound N,N'-diethyldiaminocarbene ligand. The N atom bridges Ru (1) and Ru(5) [mean 2.26(2) A] while the carbene carbon atom is bound exclusively to Ru (6) [Ru( 6)-C(3), 2.10(2) A]. In the sp2-hybridized diaminocarbene 281 7(2) -0.1286(3) -0.061 7(7) -0.1228(7) -0.20(2) -0.33( 1) -0.231(5) -0.206(3) -0.172(3 6) 2.432( 7 bonds, however, only 44 electrons are required.…”

Reactions of benzothiazolide triosmium clusters with tetramethylthiourea

“…The reactions of thiourea and a number of its derivatives with dodecacarbonyl triruthenium have attracted increasing attention because these reactions are usually associated with the cleavage of C-S, C-N, N-H and/or C-H bonds of the alkyl substituted thiourea ligands were found to give, depending upon the substituents, and the reaction conditions, a large variety of ruthenium clusters containing not only thioureato, hydrido and sulfido ligands but also carbene, dicarbene and carbyne ligands derived from the thiourea employed [18][19][20][21][22][23][24][25]. Related chemistry of N,Ndiethyl-N 0 -p-tolylthiourea with polynuclear rhenium carbonyl complexes has been reported by Adams et al [26].…”