Oxidative addition reactions of benzo[b]thiophene and dibenzothiophene with [Os3(CO)10(MeCN)2]: room-temperature ring opening of benzo[b]thiophene at triosmium clusters

An Electron-Deficient Triosmium Cluster Containing the Thianthrene Ligand: Synthesis, Structure and Reactivity of [Os3(CO)9(μ3-η2-C12H7S2)(μ-H)]

“…The FAB mass spectrum of 1 shows a molecular ion peak at m/z 1040 consistent with its formulation and fragmentation peaks due to the sequential loss of nine CO groups were also [26] as has been found for complexes derived from benzothiophene and dibenzothiophene [13,15] The solid-state molecular structure of 2 is shown in Figure 1, crystal data are given in Table 1, and selected bond distances and bond angles are listed in Table 2. The structure consists of an isosceles triangle of osmium atoms with almost two equal metal-metal edges{Os(1)-Os ( (2) edge of the triangle, sitting trans to carbonyl groups CO (13) and CO (23) [29].…”

“…The pattern of the IR spectrum of 1 in the carbonyl stretching region is very similar to that of [Os 3 (CO) 9 (μ 3 -η 2 -C 12 H 6 S)(µ-H) 2 ], which was obtained from the reaction of [Os 3 (CO) 10 (MeCN) 2 ] with dibenzothiaphene and characterized by X-ray diffraction, indicating that they are isostructural [15]. The FAB mass spectrum of 1 shows a molecular ion peak at m/z 1040 consistent with its formulation and fragmentation peaks due to the sequential loss of nine CO groups were also [26] as has been found for complexes derived from benzothiophene and dibenzothiophene [13,15] The solid-state molecular structure of 2 is shown in Figure 1, crystal data are given in Table 1, and selected bond distances and bond angles are listed in Table 2.…”

“…Both C-H and C-S bond activated products of thiophene, tetrahydrothiophene, benzothiophene and dibenzothiophene were obtained from their reactions with activated and/or unsaturated triosmium clusters [13][14][15][16]. However, the chemistry of S-heterocycles containing fused benzene rings is distinctly less developed than that of the corresponding N-heterocycles.…”

The activation and transformations of acenaphthylene by osmium carbonyl cluster complexes

“…Herein, we show that Os 3 (CO) 10 (NCMe) 2 reacts with acenaphthylene preferentially by activation of the two CH bonds on the five membered ring in a series of two steps that leads to the complexes Os 3 (CO) 10 (m-H)(mÁ/h 2 -C 12 H 7 ) (2) and Os 3 (CO) 9 (m 3 Á/h 2 -C 12 H 6 )(m-H) 2 (3). The latter contains a triply bridging acenaphthyne ligand.…”

Syntheses and Fluxional Processes of Diphenyl(2‐thienyl)phosphane Derivatives of Triosmium Clusters

“…[13][14][15] Similar results have been observed for 2-methylthiophene, 2,2Ј-bithiophene and 2,2Ј:5Ј,2ЈЈ-terthiophene. [16] The first room-temperature C-S bond cleavage of a (benzo)thiophene coordinated to a metallic cluster was reported by Arce et al [17] In chloroform at room temperature the cluster [Os 3 (µ-H)(CO) 10 (µ-C 8 H 5 S)], which contains a µ-η 2 -benzothienyl ligand, undergoes C(vinyl)-S bond cleavage to yield the cluster [Os 3 (CO) 10 (µ-C 8 H 6 S)], which contains an open benzothiophene ligand coordinated to an open Os 3 unit through a µ-S atom and a µ-η 2 -vinyl group (Scheme 2). Despite the above-mentioned examples of thiophene coordination and activation, thiophene remains a relatively poor ligand for low-valent metal complexes, and thienylphosphanes [e.g.…”