15696-40-9Relevant articles and documents
Os3(CO)11(BiPh3): The missing link in osmium-bismuth cluster chemistry
Oh, Suat Ping,Li, Ying-Zhou,Leong, Weng Kee
, p. 46 - 48 (2015)
Abstract The room temperature reaction of Os3(CO)11(NCCH3) with BiPh3 afforded the substituted derivative Os3(CO)11(BiPh3) which decomposed rapidly. The X-ray crystallographic study is reported, together with that of the stibine and arsine analogues.
Reaction of 6-methyl-2,2′-bipyridine with 1,2-Os3(CO) 10(MeCN)2: Syntheses, reductive elimination/ligand displacement kinetics, and X-ray diffraction structures of the isomeric clusters HOs3(CO)9(μ2-N2C 11H9)
Poola, Bhaskar,Carrano, Carl J.,Richmond, Michael G.
, p. 3018 - 3028 (2008)
Treatment of Os3(CO)10(MeCN)2 (1) with the heterocyclic ligand 6-methyl-2,2′-bipyridine (6-Me-2,2′-bpy) at room temperature leads to the formation of the isomeric hydride-bridged clusters HOs3(CO)9(μ2-CH2N 2C10H7) (2) and HOs3(CO) 9(μ2-N2C11H9) (3). The cyclometalation of the ancillary 6-Me group in 2 and the ortho metalation of the nonsubstituted pyridyl ring in 3 have been confirmed by spectroscopic and crystallographic methods. Thermolysis of 2 leads to the formation of 3 and the dihydride cluster H2Os3(CO)8(μ3- N2C11H8) (4); the latter cluster, whose structure has been crystallographically determined, derives from a formal loss of CO and C-H bond activation of the methylene moiety in 2. Heating 2 in the presence of ligand-trapping agents proceeds with the release of the 6-Me-2,2′-bpy ligand and formation of Os3(CO)9L 3 [where L = CO, P(OMe)3]. The kinetics for the reaction between 2 and added ligand have been investigated by UV-vis and NMR spectroscopies and found to be first-order in starting cluster and independent of the incoming ligand. Parallel kinetic experiments employing the deuterated cluster DOS3(CO)9(μ2-CD2N 2C10H7) (2-d3), which was prepared from cluster 1 and 6-Me-d3-2,2′-bpy, confirm the existence of a primary kinetic isotope effect (KIE) of 1.78 at 323 K. The KIE data and the calculated activation parameters [ΔS? = 21.7(4) kcal/mol; ΔS? = -13(1) eu] are strongly suggestive of a reaction scheme involving a rate-limiting reductive coupling of the bridging hydride ligand and cyclometalated alkyl moiety in 2 to furnish a putative sigma complex containing an intact methyl group bound to the Os3 cluster, prior to the generation of the unsaturated cluster Os3(CO)9(μ-N 2C11H10). Thermolysis of 3 in the presence of added P(OMe)3 does not furnish free 6-Me-2,2′-bpy but proceeds by a ligand-induced displacement of the methyl-substituted pyridyl ring and formation of the cluster compound HOs3(CO)9-[P(OMe) 3](μ2-N2C11H9) (5). The kinetics for the reaction between 3 and P(OMe)3 have been studied over the temperature range 333-356 K, and on the basis of the observed activation parameters [ΔH? = 13.0(3) kcal/mol; ΔS? = -30(1) eu] and the first-order dependence on the cluster and ligand, an associative process that involves P(OMe)3 ligand attack on the cluster and release of the methyl-substituted pyridyl ring in the rate-limiting step is proposed.
Morrison,E.D.,Steinmetz,G.R.,Geoffrey,G.
, p. 4104 (1983)
Triosmium and triruthenium clusters containing diazaheterocycles
Agarwala, Razaram,Azam, Kazi A.,Dilshad, Rahima,Kabir, Shariff E.,Miah, Rashid,et al.
, p. 135 - 144 (1995)
The reactions of Os3(CO)11(MeCN) with 1-vinylimidazole, imidazole and pyrazole (L-H) result in the formation of Os3(CO)11(L-H) (1, L-H = 1-vinylimidazole; 2, L-H = imidazole; 3, L-H = pyrazole) in good yields.Thermolysis of these complexes at 98 deg C gives two separable isomers of (μ-H)Os3(CO)10(μ-L).In the case of 1 and 2, these isomers are formed by the activation of the two C-H bonds adjacent to the imino nitrogen atom whereas for 3 they are formed by either a C-H or a N-H activation.These isomers interconvert at 128 deg C.The reaction of Ru3(CO)12 with 1-vinyl-imidazole and imidazole in the presence of sodium benzophenone ketyl at 67 deg C yields the cyclodimetallated compounds (7, R=CH=CH2; 8, R=H) in the same isomeric form as the minor isomers in the osmium series.All the new compounds are characterized by IR, 1H-NMR and elemental analysis together with the X-ray crystal structures of 2 and 7.Compound 2 crystallizes in the monoclinic space group P21/c with unit cell parameters a = 12.081(2) Angstroem, b = 10.539(2) Angstroem, c = 15.834(2) Angstroem, β = 102.61(2) deg, V = 1959(1) Angstroem3 and Z = 4.Least-squares refinement of 3570 reflections gave a final agreement factor of R = 0.0655 (Rw = 0.0728).Compound 7 crystallizes in the monoclinic space group P21/c with unit cell parameters a = 14.665(4) Angstroem, b = 7.5311(9) Angstroem, c = 18.291(4) Angstroem, β = 96.14(1) deg, V = 2008.5(7) Angstroem3 and Z = 4.Least-squares refinement of 3042 reflections gave a final agreement factor of R = 0.0407 (Rw=0.0749). Keywords: Osmium; Heterocycles; Cluster; Diazine; Nitrogen; Hydride
PREPARATION AND SOME REACTIONS OF μ-TRICARBONYLOSMIO-BIS-(4 Os-Os); THE MOLECULAR STRUCTURES OF (OS-Os)>(4 Os-Os)
Farrar, David H.,Johnson, Brian F. G.,Lewis, Jack,Raithby, Paul R.,Rosales, Maria J.
, p. 2051 - 2058 (1982)
The reaction of with carbon monoxide at 160 deg C and 90 atm leads to the formation of ( 1 ) in high yields.This complex crystallises in the triclinic space group P1 with a=8.880(4), b=10.244(5), c=16.529(7) Angstroem, α=99.98(2), β=93.44(2), γ=110.37(3) deg, and Z=2.The structure was solved by a combination of direct methods and Fourier-difference techniques and refined by blocked-cascade least squares to R=0.040 for 2616 observed diffractometer data.The metal-atom skeleton consists of two triangles sharing a vertex.The Os atom common to both triangles is co-ordinated to three terminal cabonyl groups, and the other four metal atoms are each co-ordinated to four carbonyl groups, two in axial and two in equatorial sites.Comp;ex ( 1 ) reacts with ligands L=P(OMe)3 (a) or PEt3 ( b ) to prosuce complexes with the general formula .On heating decarbonylates to give ( 4 ) which subsequently reacts with ligands L=CO, P(OMe)3 ( a ), or PEt3 ( b ) to produce ( 1 ), ( 5a ), and (5b ) respectively.The molecular structure of 3> ( 5a ) has been solved using the same techniques as for ( 1 ), and refined by blocked full-matrix least squares to R=0.071 for 2144 observes diffractometer data.This complex crystallises in the triclinic space group P1 with a=11.150(5), b=11.792(6), c=18.581(10) Angstroem, α=106.91(3), β=92.67(3), γ=109.45(3) deg, and Z=2.The molecular geometry resembles that of ( 1 ) except that three equatorial carbonyls on three different Os atoms have been replaced by phosphite groups.The relationsship between the structures of ( 1 ) and ( 4 ) is discussed briefly in terms of transformations of the metal cluster skeleton.These two compound represent the first case where two binary carbonyls with the smee number of metal atoms have different numbers of carbonyls bonded to them.
Synthesis of New Cobalt-Osmium Mixed-metal Clusters using a Novel Reactive Cobalt Species; X-Ray Crystal Structure of
Lewis, Jack,Pardy, Richard B. A.,Raithby, Paul R.
, p. 1509 - 1512 (1982)
Thermal decomposition of the known complex gives the intermediate species 'Co-(C5Me4Et)' which reacts with to produce .This complex crystallises in the triclinic space group P1 with a = 9.072(4), b = 10.477(5), c = 13.921(7) Angstroem, α = 95.80(3), β = 93.54(3), γ = 102.48(3) degree, and Z = 2.The structure was solved by a combination of direct methods and Fourier-difference techniques and refined by blocked-cascade least squares to R = 0.039 for 3 084 diffractometer data.The Co(C5Me4Et) fragment caps the Os3 triangle.Each Os atom is also co-ordinated to three terminal carbonyl groups while the tenth carbonyl bridges an Os-Co bond.The complex reacts with hydrogen to give , and both clusters react with carbon monoxide under fairly mild conditions to yield and .
Gubin, S. P.,Trukhacheva, V. A.,Burmakina, G. V.,Chentsova, O. M.,Ioganson, A. A.
, (1981)
Reaction of pyrones with triosmium clusters
Lin, Qi,Leong, Weng Kee
, p. 3639 - 3648 (2003)
A report on the reaction of pyrones with triosmium clusters was presented. The reactions were quantitative and were judged by infrared (IR) spectroscopy. The aromaticity of the pyrone rings was found to increase slightly and the non-carbonyl carbon adjacent to the metalation site was relatively electron-deficient.
Reactions of diacetylene ligands with trinuclear clusters. I. Reactions of 2,4-hexadiyne-1.6-diol and its dicobalthexacarbonyl derivatives with H2Os3(CO)10
Karpov, M. G.,Tunik, S.P.,Denisov, V.R.,Starova, G.L.,Nikol'skii, A.B.,et al.
, p. 219 - 226 (1995)
Reactions of H2Os3(CO)10 with the diyne ligand HOCH2C2C2CH2OH and its dicobalthexacarbonyl derivatives (μ2,η2-HOCH2C2C2CH2OH) and 2(μ2,η2:μ2,η2-HOCH2C2C2CH2OH) have been studied.The reaction of the uncomplexed ligand yields the cluster with the completely rearranged starting ligand.The structure of this compound was determined by a single-crystal X-ray study.The rearranged ligand forms a pseudo-furan ring with the C-CH3 substituent in the α-position.The reactions of H2Os3(CO)10 with the both dicobalthexacarbonyl derivatives yield the (μ-H)(μ-OH)Os3(CO)10 cluster as the main osmium-containing product.The structure of this compound was also established by a single-crystal X-ray study. Keywords: Osmium; Cobalt
Products of the Reaction of Carbon Monoxide with ; X-Ray Crystal Structure of
Farrar, David H.,Johnson, Brian F. G.,Lewis, Jack,Nicholls, J. Nicola,Raithby, Paul R.,Rosales, Maria J.
, p. 273 - 274 (1981)
The new clusters and have been prepared from the reaction of with CO; the Os atom arrangement in the former has been found to be two isosceles triangles sharing the vertex.
Synthesis and structural characterization of a triosmium carbonyl cluster containing a 9-anthracenecarbonitrile ligand derived from 9-anthraldehyde oxime
Wong, Janet Shuk-Yee,Lin, Zhen-Yang,Wong, Wing-Tak
, p. 713 - 717 (2003)
Treatment of [Os3(CO)11(MeCN)] with 1 equivalent of 9-anthraldehyde oxime in refluxing chloroform afforded a new triosmium cluster [Os3(CO)11(C14H9CN)] 1 in moderate yield. Dehydration of o
Novel higher nuclearity osmium-antimony clusters by alkene- or diene-assisted cluster condensation
Deng, Mingli,Weng, Kee Leong
, p. 1020 - 1023 (2002)
The reaction of the cluster Os3(μ-SbPh2)(μ-H)(μ3,η 2-C6H4)(CO)9, 1, with a number of alkenes and dienes led to cluster condensation to afford the novel cluster Os5(μ4-Sb)(μ-SbPh2)(μ-H)2(μ 3,η2-C6H4)(μ,η 2-C6H4)(CO)14, 3, as the major product, and another novel cluster Os5(μ4-Sb)(μ-SbPh2)(μ-H)(μ 3,η6-C6H4)(CO)14 (Ph), 4. Reaction of 3 with the Group 15 ligands EPh3 (E = P, As, Sb) afforded the corresponding monosubstituted derivatives Os5(μ4-Sb)(μ-SbPh2)(μ-H) 2(μ3,η2-C6H4) (μ,η2-C6H4)(CO)13(EPh 3), 6.
Triosmium Clusters derived from Aldehydes, Ketones, and Ketens and their Interconversions
Azam, Kazi A.,Deeming, Antony J.,Rothwell, Ian P.
, p. 91 - 98 (1981)
Acyl and enolato-complexes of types (R = CH3, C5H11, C6H13, PhCH2, Me2CH, or Ph) or (R' = H, Me, or Ph) have been obtained by oxidative addition of aldehydes at or by insertion of keten or substituted ketens into an Os-H bond of .In certain cases the interconversion of enolato- and acyl complexes was established and in other cases inferred from their reactivity.The acyl complexes where R = CH3, Ph, or PH2CH (derived from isomerisation of the enolato-complexes where R = Ph) decarbonylate at the ligand to give products derived from the alkyl complexes formed.Most acyl complexes (R = CH3, C5H11, C6H13, or PhCH2) decarbonylate, however, only at the metal with subsequent hydrogen-atom transfer to and form the ligand to give complexes of type 3-R''CCHO)H2> containing a co-ordinated formyl group.Analogous species were obtained from cyclohexanone and or from cyclohexenone and .All the complexes with organic ligands containing oxygen have Os-O bonds.
Potential models of the interactions between nitrogen-containing heterocycles and the active catalyst sites in heterogeneous hydrodenitrogenation catalysts
Eisenstadt,Giandomenico,Frederick,Laine
, p. 2033 - 2039 (1985)
At present, there is no general description of the interactions between nitrogen heterocycles and the active catalyst sites in heterogeneous hydrodenitrogenation (HDN) catalysts that promote hydrogenation and then hydrogenolysis of the C-N bond. We have attempted to model such interactions through studies of the reactions of osmium and ruthenium clusters with common HDN model substrates, including quinoline, pyridine, tetrahydroquinoline (THQ), and piperidine. Os3(CO)12 and Ru3(CO)12 with quinoline or pyridine lead to complexes of the general formula M3(μ-H:μ-Y)(CO)10 (M = Ru, Os; Y = C9H6N, C9H8N, C5H8N) or M3(μ-H:μ-Y)2(CO)8 (M = Ru, Os; Y = C5H4N, C9H6N). The reactions of Os3(CO)12 with aliphatic heterocyclic amines leads to complexes having stoichiometries of Os3(μ-H:μ-Y)(CO)10 (Y = C5H8N, C9H8N, C9H6N), Os3(μ-H)2(μ-Y)(μ-Y′)(CO)8 (Y = C9H8N, Y′ = C9H6N), or Os3(μ-H:μ-Y)2(CO)8 (Y = C9H6N), and when the heterocyclic amine is 1,2,3,4-tetrahydroquinoline (THQ), a small amount of free quinoline is also produced. As a general rule, both aliphatic and aromatic nitrogen heterocycles undergo α-metalation during reactions with both homogeneous and heterogeneous metal complexes or particles. In the case of osmium and ruthenium, metalation results in the formation of metalloazocyclobutenes even when the starting heterocycle is saturated. Thus, activation/dehydrogenation of the N-H and α-C-H bonds of secondary amines occurs readily in the systems described here. Reaction pathways for the formation of the various products and their relationships to hydrogenation and dehydrogenation catalysis are proposed.
Extrusion of selenium and tellurium atoms from selenophene and tellurophene by reaction with trinuclear iron, ruthenium, and osmium clusters: crystal structures of 3-Se)(μ4-C4H3)(CO)20> and of 3-Se)(μ-C4H4)(CO)11>
Arce, Alejandro J.,Machado, Ruben,Rivas, Carlos,Sanctis, Ysaura de,Deeming, Anthony J.
, p. 63 - 75 (1991)
The trinuclear carbonyl clusters , , , and react with selenophene and tellurophene (cyclo-C4H4X, X = Se or Te) under mild conditions to give compounds containing the open-chain ligands CHCHCHCHX or the fragments X, C4H4, C4H3, or H as bridging ligands.The following compounds were isolated and characterised: , 1 where X = Se (X-ray structure reported previously) and 8 where X = Te, , 2, , 3, , 4, , 5, , 6, and , 7.The clusters 2 and 5 were shown by single-crystal X-ray diffraction methods to have had both Se-C bonds broken to give μ3-Se ligands in each case.Compound 2 contains an interesting μ4-C4H3 ligand linking two Os3 units through a μ-alkylidyne bridge, a ?-Os-C bond, and an η3-allyl component.Compound 5 has a μ-C4H4 ligand of a type previously found to be formed by alkyne coupling.The other compounds were characterised spectroscopically.
Cage Opening of a Carborane Ligand by Metal Cluster Complexes
Adams, Richard D.,Kiprotich, Joseph,Peryshkov, Dmitry V.,Wong, Yuen Onn
, p. 6501 - 6504 (2016)
The reaction of Os3(CO)10(NCMe)2 with closo-o-C2B10H10 has yielded two interconvertible isomers Os3(CO)9(μ3-4,5,9-C2B10H8)(μ-H)2 (1 a) and Os3(CO)9(μ3-3,4,8-C2B10H8)(μ-H)2 (1 b) formed by the loss of the two NCMe ligands and one CO ligand from the Os3 cluster. Two BH bonds of the o-C2B10H10 were activated in its addition to the osmium cluster. A second triosmium cluster was added to the 1 a/1 b mixture to yield the complex Os3(CO)9(μ-H)2(μ3-4,5,9-μ3-7,11,12-C2B10H7)Os3(CO)9(μ-H)3 (2) that contains two triosmium triangles attached to the same carborane cage. When heated, 2 was transformed to the complex Os3(CO)9(μ-H)(μ3-3,4,8-μ3-7,11,12-C2B10H8)Os3(CO)9(μ-H) (3) by a novel opening of the carborane cage with loss of H2.
Stereospecific coordination of L-hydroxyproline esters with triosmium clusters
Maksakov, V. A.,Kirin, V. P.,Golovin, A. V.
, p. 1941 - 1945 (1995)
The reactions of cluster (μ-H)Os3(CO)10(μ-OH) with ethyl and isopropyl esters of L-oxyproline were studied.In the presence of Me3NO intermediate complex (μ-H)Os3(CO)9(μ-OH)L (L - isopropyl ester of L-oxyproline) is formed, which slowly converts to the more stable cluster .Cluster complexes containing chelate-bridging heterocycles were also obtained by heating (μ-H)Os3(CO)10(μ-OH) with esters of L-oxyproline.In both cases, only one of the possible diastereomeric complexes (R = Et, Pri) is formed, which indicates that the reactions are stereospecific.Based on analysis of Dreiding's models, an attempt to determine the absolute configuration of the obtained clusters was made. - Keywords: triosmium clusters, L-hydroxyproline esters, stereospecific coordination
Ferrari, R. P.,Vaglio, G. A.
, p. 141 - 144 (1976)
Non-classical NHC transfers from the reaction of (IMes)AgCl with osmium carbonyl clusters
Cooke, Craig E.,Ramnial, Taramatee,Jennings, Michael C.,Pomeroy, Roland K.,Clyburne, Jason A. C.
, p. 1755 - 1758 (2007)
N-Heterocyclic carbene transfer reactions were attempted using IMesAgCl and two osmium clusters. The products isolated from these reactions suggest that NHC transfers can be unpredictable. The Royal Society of Chemistry.
