Cluster synthesis. 4. The role of sulfido ligands in the synthesis of high nuclearity metal carbonyl cluster compounds. The synthesis of Os4(CO)133-S)2 and Os7(CO)204-S)2 and the crystal and molecular structure of Os7(CO)204-S)2

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

36 Scopus Citations
View graph of relations

Author(s)

Detail(s)

Original languageEnglish
Pages (from-to)1078-1083
Journal / PublicationOrganometallics
Volume2
Issue number9
Publication statusPublished - 1983
Externally publishedYes

Abstract

The cluster compound Os3(CO)93-S)2 has been found to react with Os(CO)5 in the presence of UV irradiation to yield the cluster Os4(CO)133-S)2 (40% yield), and Os4(CO)123-S)2 has been found to combine with Os3(CO)10(NCMe)2 when refluxed in octane solvent for 2 h to yield the new cluster compound Os7(CO)204-S)2, V (16% yield). Compound V has been characterized by a single-crystal X-ray diffraction analysis: space group P212121, a = 11.205 (5) Å, b = 14.461 (6) Å, c = 21.246 (16) Å, V = 3443 (6) Å3, Mr = 1955.7 g/cm3, Z = 4, ρcalcd = 3.77 g/cm3. The structure was solved by direct methods. Full-matrix least-squares refinement on 2315 reflections (F2 ≥ 3.0σ(F2)) yielded the final residuals RF = 0.055 and RwF = 0.044. The structure consists of a pentagonal-bipyramidal cluster of five osmium atoms and two tetracoordinate sulfido ligands. The two sulfido ligands which are not mutually bonded and three osmium atoms form the equatorial plane. Two Os(CO)4 groups bridge adjacent apical-equatorial edges of the pentagonal bipyramid on opposite sites of the equatorial plane. Two of apical-equatorial metal-metal bonds in the cluster at 2.969 (2) and 2.963 (2) Å are significantly longer than the other four, range 2.893 (2)-2.905 (2) Å. The metal-metal bonds involving the Os(CO)4 groups range from 2.801 (2) to 2.825 (2) Å. Compound V contains 20 linear terminal carbonyl ligands. The importance of sulfido ligands in the synthesis of high nuclearity metal carbonyl clusters is noted and discussed. © 1983 American Chemical Society.

Citation Format(s)

Cluster synthesis. 4. The role of sulfido ligands in the synthesis of high nuclearity metal carbonyl cluster compounds. The synthesis of Os4(CO)133-S)2 and Os7(CO)204-S)2 and the crystal and molecular structure of Os7(CO)204-S)2. / Adams, Richard D.; Horváth, István T.; Mathur, Pradeep; Segmüller, Brigitte E.; Yang, Li-Wu.

In: Organometallics, Vol. 2, No. 9, 1983, p. 1078-1083.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review