41753-97-3

Upstream product

• 15696-40-9 dodecacarbonyl triosmium 
• 603-35-0 triphenylphosphine 
• 116261-58-6 Os₃(CO)₁₁(PPh₃) 
• 1184-78-7 trimethylamine-N-oxide 
• 61817-93-4 bis(acetonitrile)decacarbonyltriosmium 
• 60146-16-9 {Os3(CO)10(cis-η4-buta-1,3-diene)} 
• 75-05-8 acetonitrile 
• 75-09-2 dichloromethane 
• 3878-44-2 Triphenylphosphine selenide 

Downstream Products

• 163159-01-1 Os3(CO)9(PPh3)2(η(2)-C60) 

Relevant academic research and scientific papers

Structural characterisation of the elusive isomer of Os3(CO)10(PPh3)2

The X-ray crystal structure of the elusive isomer of Os3(CO)10(PPh3)2 in which the two phosphine ligands are cis and trans with respect to the phosphine-substituted Os-Os edge has been determined; the first dire

Triphenylphosphine-substituted selenido and sulfido clusters of osmium derived from Ph3PSe or Ph3PS

Cleavage of PSe bonds occurs readily in the room-temperature treatment of [Os3(CO)10(MeCN)2] with Ph3PSe to give three new compounds, [Os3(μ3-Se) 2(CO)8(PPh3)] (2), [Os3(μ 3-Se)(μ3-CO)(CO)7(PPh3) 2] (5) and [Os3(μ-OH)2(CO) 8(PPh3)2] (6), respectively, and three known compounds, [Os3(μ3-Se)2(CO)9] (1), [Os3(μ3-Se)(μ-CO)2(CO) 7(PPh3)] (3), and 1,2-[Os3(CO) 10(PPh3)2] (4).No evidence for any product containing a co-ordinated Ph3PSe ligand was obtained.The analogous reaction between [Os3(CO)10(MeCN)2] and Ph 3PS produces five new compounds [Os3(μ3-S) 2(CO)8(PPh3)] (7), [Os3(μ 3-S)(μ-CO)2(CO)7(PPh3)] (8), [Os3(μ3-S)(μ3- CO)(CO) 7(PPh3)2] (9), [Os3(μ 3-)2(CO)7(PPh3)2] (11) and compound 6 in addition to the known compound 4. Treatment of 2 with Me 3NO at 50 °C gives the trinuclear cluster [Os3(μ 3-Se)2(CO)7(PPh3)(NMe3)] (13) and the hexanuclear cluster [Os6(μ3-Se) 4(CO)14(PPh3)2] (12). Treatment of compound 1 with PPh3 and Me3NO at room temperature gives [Os3(μ3-Se)2(CO)7(PPh 3)2] (10). Compound 2 reacts with PPh3 similarly to give 10. Compound 3 reacts with elemental selenium at 110 °C to give 2. The new compounds 2, 5, 6 and 8 were characterized by single-crystal X-ray diffraction. The compounds 3, 5, 8 and 9 contain Os3(μ 3-S) or Os3(μ3-Se)cluster cores with three metal-metal bonds while 2, 7, 10, 11 and 12 contain Os3(μ 3-S)2or Os3(μ3-Se)2 cores two metal-metal bonds. The two hydroxy ligands in the triosmium cluster 6 bridging the open osmium-osmium edge and are probably derived from water. A study of the dynamic exchange of PPh3 ligands in 5 is also reported.

REACTIVITY OF (M = Ru, Os) TOWARDS ORGANIC AND ORGANOMETALLIC ELECTROPHILES; EVIDENCE FOR ELECTROPHILIC endo-ATTACK AT THE PHOSPHIDO MOIETY OF

Electrophilic attack on the bridging phosphido moiety of (1) allows the formation of new phosphorus-containing compounds.The phosphido clusters (R = (CH2)6I (2a), (CH2)10I (2b), C4H8OH (2c), HOs3(CO)10(PPh3) (4a), HOs3(CO)10 (4b) have been synthesized by the reaction of 1 with the appropriate electrophiles.When R = alkyl, both exo- and endo-isomers are formed.The formation of both isomers indicates that endo-attack plays a significant role in these reactions.When R = (μ-H)Os3(CO)10(PR3) the exo-isomers are the exclusive products.Reaction of the ruthenium analogue of 1 with leads to the formation of 4-P)> (6).The crystal structure of (μ3-PH)> (4b) is presented.Key words: Phosphido moiety, cluster, Osmium, Ruthenium, electrophilic attack, isomer.

Oxygen atom transfer to metal carbonyls. Kinetics and mechanism of CO substitution reactions of M3(CO)11L (M = Fe, Ru, Os) in the presence of (CH3)3NO

The rates and activation parameters are reported for CO-substitution reactions of M3(CO)11L (M = Fe, L = P(OEt)3, P(OMe)3; M = Ru, Os, L = P(OEt)3, P(OMe)3, P(n-Bu)3, PPh3, AsPh3, SbPh3) in the presence of (CH3)3NO. The rates of reaction are second order, first order in (CH3)3NO concentration, first order in M3(CO)11L concentration, and zero order in entering ligand concentration. For phosphite derivatives, the relative rates are M3(CO)11P(OMe)3 > M3(CO)11P(OEt)3. For other ligand-substituted complexes, the rates of reaction increase with increasing stretching frequency of the CO bands in the IR spectra. The mechanism involved appears to be similar to that proposed earlier of attack by the O atom of (CH3)3NO on a C atom of a CO coordinated to an unsubstituted metal atom. The unexpected slow rates for the reactions of M3(CO)11P(OR)3 are discussed in terms of shorter M-M bond distances in the cluster.

Cluster chemistry LV. Stereochemistry of group 15 ligand-substituted derivatives of M3(CO)12 (M = Ru, Os). A. X-Ray structures of six complexes M3(CO)11(L) (M = Ru, L = PPh(OMe)2, P(OCH2CF3)3, P(OCH2)3CEt and AsPh3; M = Os, L = PPh3 and PPh(OMe)2)

X-ray crystal structures of six complexes M3(CO)11(L) (M = Ru, L = PPh(OMe)2, P(OCH2CF3)3, P(OCH2)3CEt and AsPh3; M = Os, L = PPh3 and PPh(OMe)2) have been determined.Consideration of these results, together with other published data, allowed several conclusions to be drawn concerning the effect of substituting one CO group in M3(CO)12 (M = Ru, Os) by a P- or As-donor ligand.The most important are that L occupies an equatorial site, the M-M separation cis to L increases with increasing cone angle of L, while the COeq ligand cis to L on the same metal atom is more tightly bound.Distortions of the M3L12 molecule from D3h to D3 geometry appear to be related to the ?-donor properties of L.The reactions between Ru3(CO)12 and P(OCH2CF3)3, and between Os3(CO)12 and PPh3 or PPh(OMe)2, to give M3(CO)12-n(L)n (n = 1-3), are described.Crystal data: Ru3(CO)11, monoclinic, P21/c, a 9.647(3), b 20.529(7), c 14.692(5) Angstroem, β 119.93(2) deg, U 2522(1) Angstroem3, Z = 4, N0 (observed data, with I>3?(I)) = 5829, R = 0.035, R' = 0.037; Ru3(CO)11, triclinic, P1, a 12.920(1), b 11.530(2), c 10.189(1) Angstroem, α 85.93(1), β 86.57(1), γ 70.66(1) deg, U 1427(1) Angstroem3, Z = 2, N0 = 4061, R = 0.038, R' = 0.054; Ru3(CO)11, monoclinic, P21/c, a 13.57(1), b 14.779(1), c 12.362(3) Angstroem, β 98.34(4) deg, U 2453(1) Angstroem3, Z = 4, No= 5950, R = 0.039, R' = 0.054; Ru3(CO)11(AsPh3), monoclinic, C2/c, a 22.496(6), b 16.348(4), c 17.345(5) Angstroem, β 103.65(2) deg, U 6198(3) Angstroem3, Z = 8, No= 6071, R = 0.032, R' = 0.028; Os3(CO011(PPh3), monoclinic, C2/c, a 22.196(5), b 16.265(3), c 17.370(5) Angstroem, β 103.86(2) deg, U 6088(33) Angstroem3, Z = 8, No= 4125, R = 0.031, R' = 0.033; Os3(CO)11, monoclinic, P21/c, a 10.817(3), b 14.993(4), c 16.174(3) Angstroem, β 101.87(2) deg, U 2567(1) Angstroem, Z = 4, No = 5506, R = 0.047, R' = 0.057.

Synthesis and Reactions of a New Isomer of 2>

The isomeric butadiene compounds 4-s-cis-C4H6)> and react with P(OMe)3 at room temperature to give 1,1- and 1,2-isomers of 2>, whereas PPh3 reacts with the butadiene compounds to give only the known 1,2-isomer. 1,1-2>, which has been characterised by infrared, 31P and 13C NMR data, reacts with trifluoroacetic acid to give the singly protonated cation 1,1-2>(+) isolated in good yield as the hexafluorophosphate salt.

Substitution Kinetics of and

The kinetics of reactions of and with P- or As-donor ligands in p-xylene or toluene have been studied and shown to be characteristic of reversible dissociative processes.In both cases MeCN is ca. 10 times more nucleophilic towards the reactive intermediate than is PPh3.Activation parameters confirm the weakness of the Os-NCMe bonds and suggest that loss of the first MeCN from may be a concerted process in which a 'sideways on' bridging CO replaces the leaving MeCN.The strength of bridge bonding can be estimated to be >= 30kJmol-1.

Systematic Synthesis of Tetranuclear Osmium Clusters by the Reaction of Trinuclear Clusters with ; Crystal Structure of

The complex reacts with the clusters 12-n(MeCN)n> (n=1 or 2) to afford tetranuclear species (1) and (2), respectively.The pyrolysis of (2) leads to the formation of via the intermediate .The acetonitrile ligand of complex (2) is readily displaced by P(OMe)3 to give > (3) along with small quantities of 2> and 3>.With PPh3 the reaction is so slow that fragmentation occurs and the only product isolated is .The hydride-coupling reaction also occurs between and (X=Cl, Br or I) and the complexes obtained have been fully characterised.These complexes decompose in solution via loss of HX to afford .The reaction between and proceeds smoothly for R=Me (7) or Ph (8) but for R=H the major product isolated is .All the products were characterised by i.r., 1H and 13C n.m.r. spectroscopy and structural assignments made.The structure of the cluster (5) was confirmed by an X-ray analysis and shown to consist of an Os3 triangle with a pendant OsH(CO)4 unit co-ordinated to it.One edge of the triangle is bridged by both a hydride and a bromide ligand while another edge is bridged by a hydride.

Trinuclear Osmium Clusters as Models for Intermediates in Carbon Monoxide Reduction Chemistry. 1. Stepwise Reduction of CO to a μ-CH2 Ligand on an Os3 Cluster Face

Treatment of Os3(CO)12 in tetrahydrofuran (THF) with K at 0 deg C gives an unstable formyl complex K (1).Acidification of THF solutions of 1 with aqueous 20percent H3PO4 yields the new cluster Os3(CO)11(μ-CH2) which has been spectroscopically characterized.Attempted alkylation of 1 with BF4 also gave Os3(CO)11(μ-CH2).Methane is produced when Os3(CO)11(μ-CH2) is heated under an H2 atmosphere, but when the mixture is heated in the absence of H2, CO loss occurs to yield H2Os3(CO)9(μ3-CCO), which has been spectroscopically characterized.The mechanism of the - to Os3(CO)11(μ-CH2) transformation is discussed as well as the possible relevance of these results to CO reduction on metal surfaces.