15696-40-9Relevant academic research and scientific papers
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.
Multicenter transformations of the methyl ligand in CH3Os3Au carbonyl cluster complexes: Synthesis, characterization and DFT analyses
Adams, Richard D.,Luo, Zhongwen,Chen, Mingwei,Rassolov, Vitaly
, p. 95 - 107 (2016)
Os3(CO)11(NCCH3) and Os3(CO)10(NCCH3)2 react with (CH3)AuPPh3 to yield the new Os3Au cluster complexes, Os3(CO)10(μ-O=CCH3) (AuPPh3), 1 and Os3(CO)9(μ-η3-CH) (μ-H)2(μ-AuPPh3), 2 containing bridging acetyl and bridging methylidyne ligands, respectively, by two competing reaction pathways: 1) a methyl migration/CO insertion pathway that produces a complex with a bridging acetyl ligand. and 2) C-H bond cleavage transformations via a series of decarbonylated intermediates containing an agostically coordinated bridging methyl group, a bridging methylene group, a triply bridging methylidyne ligand and bridging hydride ligands. It has also been found that carbon monoxide can induce shifts of the bridging hydride ligands back to methylidyne ligand in 2 with subsequent cleavage of Os-Au and Os-Os bonds to yield two open cluster complexes (CH3)Os3(CO)12AuPPh3, 4 and (CH3)Os2(CO)8AuPPh3, 5 having terminally coordinated methyl ligands. The open cluster complex 4 can be converted back to 1 and 2 via decarbonylation process by using either thermal or irradiation treatments. The CO dissociation mechanisms related to the CH bond transformation processes were studied by DFT computational analyses. It has been demonstrated that the Os3Au(CH3) cluster provides a robust platform to studying multicenter C-H bond transformations and for C-C bond formation via methyl migration/CO insertion processes.
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.
Mercury-osmium carbonyl clusters resulting from facile Hg-C bond cleavage: Reactions of [Os3H2(CO)10] with [Hg(C≡CPh)2] and [RHgC≡CHgR] (R = Ph, Me or Et)
Au, Yat-Kun,Wong, Wing-Tak
, p. 899 - 911 (1996)
Reaction of the unsaturated cluster [Os3H2(CO)10] with Hg(C≡CPh)2 afforded two new Os-Hg clusters cis-[Os(CO)4{(μ-Hg)Os3(CO)10(μ-η 2-CH=CHPh)}2] 1 and [{Os3(CO)10(μ-η2-CH=CHPh)} 2(μ4-Hg)] 2 in 30 and 20% yield, respectively. Cluster 1 consists of two (μ-Hg)Os3(CO)10(μ-η2-CH=CHPh) subunits bonded to a central Os(CO)4 moiety in the cis configuration which under ambient conditions converts into 2 over 3-5 d with the extrusion of a HgOs(CO)4 unit. Cluster 2 comprises two skewed Os-Hg metal butterflies sharing a common wingtip Hg atom. In refluxing tetrahydrofuran (66°C) 2 underwent redistribution with the symmetrical mercurials [Hg{M(CO)3(η5-C5H5)} 2] (M = Cr, Mo or W) to afford respectively the heterometallic clusters [{Os3(CO)10(μ-η2-CH=CHPh)}(μ 3-Hg){M(CO)3(η5-C5H 5)}] (M = Cr 3, Mo 4 or W 5) in moderate yield. Alternatively, 3-5 can be obtained more readily from the reaction of cluster 1 with the corresponding symmetric mercurials at room temperature. Reactions of [Os3H2(CO)10] with [RHgC≡CHgR] (R = Ph, Me or Et) afforded the clusters [{Os3(CO)10(μ-η2-CH=CH 2)}(μ4-Hg){Os3(CO)10(μ-H)}] 6 (12%) and [{Os3(CO)10(μ-η2-CH=CH 2)}2(μ4-Hg)] 7 (25%). Cluster 7 is isostructural with 2, whilst 6 bears a central Hg atom connecting two structurally different osmium triangles. Clusters 1, 2, 6 and 7 all result from Hg-C bond cleavage of the parent organomercury species, hence the generality of this cleavage is demonstrated. The new clusters 1, 2, 4, 6 and 7 have been fully characterised by both spectroscopic and crystallographic techniques.
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
Synthesis, structure, and ligand dynamics of triosmium imidoyl clusters and their isocyanide derivatives
Day, Michael,Espitia, David,Hardcastle, Kenneth I.,Kabir, Shariff E.,McPhillips, Tim,Rosenberg, Edward,Gobetto, Roberto,Milone, Luciano,Osella, Domenico
, p. 2309 - 2324 (1993)
The synthesis of (μ-H)(μ-η2-C=NCH2CH2CH 2)Os3(CO)10 (10), the coproduct (μ-H)(μ-η1-NCH2CH2CH 2CH2)Os3(CO)10 (9) and the related imidoyl cluster (μ-H)(μ-η2-CH3CH2C=NCH 2CH2CH3)Os3(CO)10 (11) are reported. Thermolysis of 9 at 98°C yields 10 quantitatively, and both 10 and 11 are decarbonylated thermally or photochemically to yield μ3-imidoyl clusters (μ-H)(μ3-η2-C=NCH2CH 2CH2)Os3(CO)9 (2) and (μ-H)(μ3-η2-CH3CH 2C=NCH2CH2CH3)Os 3(CO)9 (3), respectively. The reactions of 2 and 3 with RNC (R = CH3, C(CH3)3) are reported, and in both cases initial adducts (μ-H)(μ-η2-C=NCH2CH2CH 2)Os3(CO)9(CNR) (R = CH3, 12; R = C(CH3)3, 13) and (μ-H)(μ-η2-CH3CH2C=NCH 2CH2CH3)Os3(CO)9(CNR) (R = CH3, 14; R = C(CH3)3, 15) are isolated in high yield. Thermolysis of 12-15 at 128°C yields the μ3-imidoyl complexes (μ-H)(μ3-η2-C=NCH2CH 2CH)2Os3(CO)8(CNR) (R = CH3, 16; R = C(CH3)3, 17) and (μ-H)(μ3-η2-CH3CH 2C=NCH2CH2CH3)Os 3(CO)8(CNR) (R = CH3, 18; R = C(CH3)3, 19). Variable temperature 1H- and 13C-NMR and 1H- and 13C-EXSY experiments are reported for 2, 10, and 16-19 which reveal, in detail, the multistage nature of the ligand exchange processes. In solution, complexes 12-19 exist as a large number of positional isomers which do not interconvert in the case of 12-15 but which are interconverted by the motion of the μ3-imidoyl ligand and axial-radial exchange in 16-19. Solid-state structures for 2, 9, 12, 13, and 16 are reported. Compound 2 crystallizes in the monoclinic space group P21/m with unit cell parameters a = 7.681(1) A?, b = 14.801(2) A?, c = 8.157(2) A?, β = 106.06(1)°, V = 891(1) A?3, and Z = 2. Least-squares refinement of 2179 reflections gave a final agreement factor of R = 0.044 (Rw = 0.043). Compound 9 crystallizes in the triclinic space group P21 with unit cell parameters a = 9.294(3) A?, b = 15.758(5) A?, c = 7.406(2) A?, α = 81.10(2)°, β = 76.47(2)°, γ = 74.88(2)°, V = 992(1) A?3, and Z = 2. Least-squares refinement of 2677 reflections gave a final agreement factor of R = 0.037 (Rw = 0.044). Compound 12 crystallizes in the monoclinic space group P21/n with unit cell parameters a = 8.987(2) A?, b = 16.067(2) A?, c = 14.436(3) A?, β = 93.06(1)°, V = 2081(1) A?3, and Z = 4. Least-squares refinement of 2579 reflections gave a final agreement factor of R = 0.051 (Rw = 0.057). Compound 13 crystallizes in the monoclinic space group P21/c with unit cell parameters a = 9.216(1) A?, b = 19.372(5) A?, c = 15.176(3) A?, β = 116.38(2)°, V = 2427(2) A?3, and Z = 4. Least-squares refinement of 4673 reflections gave a final agreement factor of R = 0.044 (Rw = 0.053). Compound 16 crystallizes in the triclinic space group P21/c with unit cell parameters a = 8.574(4) A?, b = 15.660(6) A?, c = 8.437(2) A?, α = 80.69(4)°, β = 67.12(4)°, γ = 74.09(4)°, V = 1002(1) A?3, and Z = 2. Least-squares refinement of 3738 reflections gave a final agreement factor of R = 0.058 (Rw = 0.061).
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.
Reactivity of the heteronuclear cluster RuOs3(μ-H)2(CO)13 with indene
Tan, Yong Leng Kelvin,Leong, Weng Kee
, p. 768 - 773 (2007)
The heteronuclear cluster RuOs3(μ-H)2(CO)13 (1) reacts with indene under thermal activation to afford the novel clusters RuOs3(μ-H)(CO)9(μ-CO)2(η 5-C9H7) (3), RuOs3(μ-H)(CO)9(μ3,η 5:η2:η2-C9H7) (4) and Ru2Os3(μ-H)(CO)11(μ3, η5:η2:η2-C9H 7) (5), the latter two possessing indenyl ligands in the μ3,η5:η2:η2 bonding mode. Cluster 5 exists as a mixture of two isomers. The inter-relationship among the clusters has also been investigated.
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 .
A zwitterionic triosmium cluster bearing a metallated azulene ligand coordinated perpendicularly as an alkylidene bridge
De Sanctis, Ysaura,Arce, Alejandro J.,Ca?avera, Farrah,Machado, Ruben,Deeming, Antony J.,González, Teresa,Galarza, Esperanza
, p. 2025 - 2028 (2004)
The cluster [Os3(CO)10(MeCN)2] reacts readily with azulene in refluxing cyclohexane to give the oxidative addition product [Os3(μ-H) (μ2-η1- C10H7) (CO)10] 1 which was shown by its X-ray crystal structure to contain the C5 ring of the azulenyl ligand bonded through a single carbon atom at the 1-position. We propose that the compound is zwitterionic, with the 7-membered ring a tropylium cation and the 5-membered ring coordinated as a μ-alkylidene to the metal cluster, which carries a formal negative charge. Thermal loss of one CO ligand leads by further oxidative addition to the known cluster [Os3(μ-H)2 (μ3-η1: η1:η1- C10H6) (CO)9] 2.
