Structural studies on polynuclear osmium carbonyl hydrides. 23. Vibrational study and crystal structure of (.mu.-hydrido)(.mu.-formato)decacarbonyltriosmium (.mu.-H)(.mu.-O2CH)Os3(CO)10

Abstract

3295of the rather specific requirements for halide binding both within and between the clusters. For this reason ternary systems have also been under investigation, leading to the discovery of C S N~~I~~~~~ the present CsZr6114 as sort of an intercalate of a known structure type, and, recently, the analogous NaNb6Cl15 with the Nb6CllS structure and a new structure type for CsNb6C11s.30 Obviously the use of a higher-valent second metal, especially with the electron-poorer clusters, seems attractive, for example, with MZr6114, where M = Ba would give a cluster isoelectronic with Zr6112.(30) Imoto, H.; Simon, A., private communication, 1981. Doubtlessly, less obvious derivatives will be found as well.Acknowledgment. The authors are indebted to R. A. Jacobson for continued crystallographic advice, to R. G. Barnes and D. T. Torgeson for assistance in ESR measurements, and to D. M. P. Mingos and P. Minshall for assistance in the computation, time for which was provided by the

Reactions of Os3(CO)12 with carboxylic acids in a microwave reactor; synthesis of Os2(benzoate)2(CO)6, a dinuclear osmium(I) compound with aromatic carboxylate ligands

“…The molecular geometry was shown to have approximate C 2v symmetry with cis bridging carboxylate ligands as illustrated by structure A in Chart 1. Spectroscopic evidence suggests that the other Os 2 (m-O 2 CR) 2 (CO) 6 compounds have a similar structural arrangement. To our knowledge, there have been no reports of direct reactions of aromatic carboxylic acids with Os 3 (CO) 12 .…”

“…Lewis, Johnson and coworkers discovered in 1969 that the diosmium(I) compounds Os 2 (m-O 2 CR) 2 (CO) 6 , R ¼ Me (1) or Et (2) could be synthesized by heating a mixture of Os 3 (CO) 12 and neat acetic acid or neat propionic acid in a sealed Carius tube at 185 C [1]. Compound 1 was produced in 76% yield after 5 h of heating, and 2 was prepared in 70% yield after 14 h of heating.…”

“…Compound 1 was produced in 76% yield after 5 h of heating, and 2 was prepared in 70% yield after 14 h of heating. In 1987, Deeming et al employed the same method to synthesize Os 2 (m-O 2 CCHMe 2 ) 2 (CO) 6 in 71% yield after 6 h of heating in isobutyric acid [2]. In 1988, Deeming's group showed that heating a mixture of Os 3 (CO) 12 and trifluoroacetic acid at 120 C for only 2 h produced Os 2 (m-O 2 CCF 3 ) 2 (CO) 6 in 50% yield, while heating at higher temperatures led to the formation of mononuclear products [3].…”

“…To date, only these four aliphatic carboxylic acids have been used to prepare Os 2 2þ compounds. An X-ray crystallographic analysis of Os 2 (m-O 2 CMe) 2 (CO) 6 was carried out by Bullitt and Cotton in 1971 [4]. The molecular geometry was shown to have approximate C 2v symmetry with cis bridging carboxylate ligands as illustrated by structure A in Chart 1.…”

Structure of (μ-acetato-1κO:2κO')-nonacarbonyl-1κ3C,2κ3C,3κ3C-μ-hydrido-(triphenylphosphine-3κP)-triangulo-triosmium(3 Os–Os) cyclohexane solvate

“…The normalized structure factor statistics favoured the centrosymmetric space group P1 and the subsequent analysis confirmed this. The Os atoms were located using the direct methods strategy (EEES) Shapley, St. George, Churchill & Hollander, 1982), where the hydride and bidentate ligand both bridge the same longest edge of the triosmium unit. Rather, the similarity is with the phosphine-substituted cluster OsaH(S2CH)(CO)q(PMeEPh) (Adams & Selegue, 1980), where the analogous distance with the larger donor atoms is elongated to 2.854 A.…”