1,1,2,2,2,2,3,3,3,3-Decacarbonyl-1-(η-cyclohexa-1,3-diene)-triangulo-triosmium: a novel intermediate in synthetic osmium cluster chemistry

Abstract

DecacurbonyZ-l-(~-cyelo~exa-1,3-diene)-triangulo-triosnziunz, [Os,(CO) ,,(C,H,>] (1) .-The compound [Os3(CO),,H,] (500 mg) was added to distilled refluxing n-hexane containing an excess of cyclohexa-1,3-diene or -1,4-diene under nitrogen. After 4 h, the solvent and excess diene were removed in vacuo and the 4 residue was chromatographed on silica plates using hexanediethyl ether (19 : 1) as eluant. The required compound was removed from the plates as an intense orange band and was recrystallized from hexane at -25 "C, yield 60% (Found: C, 20.7; H, 0.9. C,,H,0,,0s3 requires C, 20.5; H I 0.85%). diertyZ)-triangulo-triosnziunzTetrufluoroborate, [Os,(CO),,-(C,H,)] [BFa], (2) .-Compound (1) (30 mg) dissolved in dry dichloromethane (5 cm3) was added to [CPh,][BF,] (100 mg)

On the Ambiphilic Reactivity of Geometrically Constrained Phosphorus(III) and Arsenic(III) Compounds: Insights into Their Interaction with Ionic Substrates

“…It is also worth noting that the substrates cope of such compounds includes molecules such as ammonia,which hashistorically provendifficult to activate using precious metalc atalysts due to the unfavourable coordination/activation equilibrium. Newr outes resultingi nt he activation of NÀHb onds in ammonia are particularly appealing, becauseo ft he dearth of transition-metal systems capable of effecting such at ransformation, [7][8][9][10][11][12][13][14][15][16][17][18][19] and the relevance of NÀHa ctivation to an umber of potentially important industrialp rocesses. [20] More recently,g eometrically constrained compounds based on phosphorus(III) have also received significant attention in this field.…”

Complexation and C–H bond activation of 1,5-cyclooctadiene on triosmium carbonyl clusters

“…Previously, the diene complexes Os 3 (CO) 10 (g 4 -cyclohexadiene) [13] and Os 3 (CO) 10 (g 4 -norbornadiene) [11] were prepared in a same reaction fashion, while Os 3 (CO) 10 (g 4 -butadiene) was obtained by treating H 2 Os 3 (CO) 10 with excess butadiene [9]. Although the isolation of 1 was mentioned [10], no spectroscopic data have been reported.…”

“…It turns out that Os 3 (CO) 11 (NCMe) and Os 3 (CO) 10 (NCMe) 2 are among the most valuable reagents for the synthesis of a wealth of new triosmium cluster complexes. Shapley and co-workers [9][10][11], and Lewis and co-workers [12,13] have previously studied the reactions of H 2 Os 3 (CO) 10 and Os 3 (CO) 10 (NCMe) 2 with a variety of conjugated dienes. In this paper, we wish to report the synthesis of Os 3 (CO) 10 (g 4 -C 8 H 12 ) (1), which contains a non-conjugated 1,5-cyclooctadiene ligand, from Os 3 (CO) 10 (NCMe) 2 and its reactivity.…”

E–H Bond Activation of Ammonia and Water by a Geometrically Constrained Phosphorus(III) Compound

“…[8] New routes resulting in the activation of NÀHb onds in ammonia are particularly appealing because of the dearth of transition-metal systems capable of effecting such atransformation [9][10][11][12][13][14][15][16][17][18][19][20][21] and the relevance of N À H activation to an umber of potentially important industrial processes. [22] In addition to these high profile examples,r ecent studies have shown that complexes of phosphorus(III) with distorted geometry can cleave arange of polarized EÀHbonds (E=Oor N).…”

“…[9][10][11][12][13][14][15][16][17][18][19][20][21] Therefore,a dvances in main group mediated activation of ammonia are of great interest. [4, 5, 6c-d,24, 26, 27, 30-32] Ther eaction of 1 with ammonia gas (1 atm) results in the quantitative conversion of 1 to anew product, 2 (Scheme 2).…”