Cluster [Os3 Research Articles

Cluster build-up using the [Os(η6-C6H6)(MeCN)3]2+cation; synthesis and structural characterisation of some hexa- and hepta-nuclear arene-substituted clusters

Reactions of the cluster dianion [Os5(CO)15]2– with [Os(η6-C6H6)(MeCN)3]2+ and [Os(C6H5Me)(CF3SO3)2] provided [Os6(CO)15(η6-C6H6)]1 and [Os6(CO)15(η6-C6H5Me)]2, respectively, in good yield (≈45%). Reduction of the hexaosmium cluster [Os6(CO)18] with K–Ph2CO gave the cluster dianion [Os6(CO)17]2–3 in quantitative yield. When this dianion was treated with [Os(η6-C6H6)(MeCN)3]2+ the heptanuclear cluster [Os7(CO)17(η6-C6H6)]4 was obtained in fair yield, while the corresponding reaction with [Os(η6-C6H5Me)(CF3SO3)2] gave [Os7(CO)17(η6-C6H5Me)]5 in similar yield (ca. 25%). The four arene clusters have been characterised by spectroscopic techniques, and the molecular geometries of 1, 2 and 4 established by single-crystal X-ray diffraction techniques. In both 1 and 2 the metal framework geometry is best described as a bicapped tetrahedron. In 1 the η6-C6H6 ligand occupies a site on the central Os4 tetrahedron while in 2 in the η6-arene is co-ordinated to one of the capping Os atoms. The metal framework in 4 may be viewed as derived from a bicapped tetrahedron with the seventh metal capping one of the caps to give a chain of four fused tetrahedra. The η6-C6H6 ligand in 4 occupies a similar site to that found in 1.

The initial photochemical process of triosmiumdodecacarbonyl adsorbed on the surface of silica as studied by picosecond diffuse reflectance laser photolysis and matrix isolation

The transient absorption spectrum of the coordinatively unsaturated trinuclear osmium carbonyl cluster Os 3(CO) 11 adsorbed on the surface of silica was observed for the first time by the ps time-resolved diffuse reflectance laser photolysis of Os 3(CO) 12. The present results demonstrated that Os 3(CO) 11 is the photoprimary product responsible for the net oxidative addition of surface hydroxyls to Os 3(CO) 12 adsorbed on the surface of silica to form the surface attached trinuclear species HOs 3(CO) 10-OSi. It was revealed that the addition of surface hydroxyls to Os 3(CO) 11 is completed within the time of our instrumental response (⩽35 ps), which is comparable to the coordination of solvent to coordinatively unsaturated metal carbonyls.

Mixed alkyne-arene-substituted carbonyl clusters; the crystal and molecular structure of OS 4(CO) 9(η 6-C 6H 6)(MeCCMe)

Reaction of the alkyne-substituted cluster anion [Os 3(CO) 9(R 1CCR 2)] 2− with the cation [Os(η 6-C 6H 6)(CH 3CN)] 2+ affords the neutral tetranuclear cluster Os 4(CO) 9(η 6-C 6H 6)(R 1CCR 2) (R 1=R 2=Me ( 1a); R 1=Me, R 2=Ph ( 1b); R 1=R 2=Ph ( 1c)). The structure of 1a has been confirmed by a single-crystal X-ray analysis. The metals adopt a ‘butterfly’ geometry with the alkylenic CC vector parallel to the ‘hinge’ vector of the ‘butterfly’, and the η 6-C 6H 6 ligand occupies a terminal site on one of the ‘wingtip’ Os atoms. Complexes 1a and 1b may also be prepared by the reaction of the activated arene cluster Os 4H 2(CO) 9(η 6-C 6H 6)(CH 3CN) with MeCCMe and MeCCPh, respectively. Under similar reaction conditions, with PhCCPh, the arene and acetonitrile ligands are substituted by the alkyne to give the known complex Os 4H 2(CO) 9(PhCCPh) 2 ( 2c).

Synthesis, and 19F NMR and X-ray structural studies of triosmium clusters (μ-H)Os 3(CO) 10L[ON(CF 3) 2] (L  PPh 3, AsPh 3 and SbPh 3)

Bis(trifluoromethyl)nitroxyl radical reacts with H 2Os 3(CO) 10L (L  PPh 3, AsPh 3, SbPh 3) to afford the derivatives (μ-H)Os 3(CO) 10L[ON(CF 3) 2] in which the (CF 3) 2NO moiety is revealed by single crystal X-ray determinations to assume an axial position. Variable-temperature 19F NMR spectral studies indicate that the two CF 3 groups of the(CF 3) 2N moiety become magnetically different at lower temperature due to restricted rotation about the NO bond. The activation energies estimated from the coalescence temperatures are 54.4 and 52.3 kJ/mole for (μ-H)Os 3(CO) 10PPh 3[ON(CF 3) 2] and for (μ-H)Os 3(CO) 10AsPh 2-[ON(CF 3) 2] respectively.

Protonation of Os3(?-H)(CO)9(?3-?,?2-C?C-R) clusters (R=CMe2OH, C(Me)=CH2)

Protonation of triosmium clusters Os3(μ-H)(CO)9(μ3-σ,η2-C≡C-R) (R=CMe2OH, C(Me)=CH2) affords a cationic complex containing a six-electron propargyl ligand which has been detected for the first time.

Oxidative Addition of Phospholes and Phosphabenzene into Triosmium and Triruthenium Clusters. Ring Opening Versus C-H Bond Cleavage

Abstract The five-membered heterocycles compounds 3,4-dimethyl-1-phenylphosphole (PhPCH[dbnd]CMeCMedbnd;CH) and 1-phenylphosphole (PhPCH[dbnd]CHCH[dbnd]CH) react with the clusters [Os3(CO)11(MeCN)] or [Os3(CO)10(MeCN)2] to give the simple substitution products [Os3(CO)12-x (phosphole)x] (x= 1 or 2), in which the phospholes are coordinated as tertiary phosphines through the phosphorus atoms. The six membered heterocyclic compounds phosphabenzene and 2-terbutyl-phosphabenzene react with [Os3(CO)11(MeCN)] or [Os3(CO)10(MeCN)2] to give simple substitution products [Os3(CO)12-x(phosphabenzene)x] (x=1 or 2). [Ru3(CO)12] and [Os3H2(CO)10] react with 2-terbutyl-phosphabenzene to give the nonacarbonyl species [HRu3(CO)9(Pdbnd;CCH[dbnd]CH[dbnd]CH[dbnd]C{tBu})] and [H2Os3(CO)9(PCHCH[dbnd]CHCH[dbnd]C{tBu})] respectively, where a C[dbnd]H bond cleavage has ocurred and the phosphorus atom is coordinated to a metal center, even though the clusters show different geometries, which are discussed.

Cluster chemistry: LXXXVII. Some homo- and hetero-nuclear complexes derived from C 2(PPh 2) 2: Crystal structures of Re 3(μ-H) 3(μ-dppa)(CO) 10 {dppa = C 2(PPh 2) 2}, Re 3(μ-H) 3(CO) 11{PPh 2[μ-C 2Ru 2(μ-PPh 2)(CO) 6]} and Os 3Ru 2(μ 5-C 2PPh 2)(μ-PPh 2)(CO) 13

Reaction of two equivalents of Re 3(μ-H) 3(CO) 11(NCMe) with dppa produces the complex {Re 3(μ-H) 3(CO) 11} 2(μ-dppa) ( 2). When an excess of dppa is used, mono-substituted Re 3(μ-H) 3(CO) 11(dppa) ( 3) and Re 3(μ-H) 3(μ-dppa)(CO) 10 ( 4) were produced. When 3 is treated with Ru 3(CO) 12, the complex {Re 3(μ-H) 3(CO) 11}(μ-dppa){Ru 3(CO) 11} ( 5) is produced in high yield. When 5 is heated, the complex Re 3(μ-H) 3(CO) 11{PPh 2[μ-C 2Ru 2(μ-PPh 2)(CO) 6]} ( 6) is produced. Using the same methodology, {Os 3(CO) 11}(μ-dppa){Ru 3(CO) 11} (bd8} and {Os 3(CO) 11}(μ-dppa){Re 3(μ-H) 3(CO) 11} ( 11) were prepared. When 8 is heated, the heteronuclear M 5 cluster Os 3Ru 2(μ 5-C 2PPh 2)(μ-PPh 2)(CO) 13 ( 10) is produced. Complexes 4, 6 and 10 were identified by single crystal X-ray studies.

Isolation and structural characterisation of Os 5(CO) 18, a postulated intermediate in the conversion of Os 5(CO) 19 into Os 5(CO) 16

The binary carbonyl cluster Os s5(CO) 18 has been obtained from the room temperature reaction of Os 3(CO) 10(MeCN) 2 with H 2 Os 3-(CO) 12. X-Ray structural analysis of the cluster shows that it has an unusual metal framework, consisting of a five metal planar ‘raft’.

Synthesis and X-ray structure of the octaosmium carbido cluster Os 8C(CO) 22

Solid state vacuum pyrolysis of Os 3H 3(CO) 9(μ 3-COMe) ( 1) gives the dark purple octanuclear carbido cluster Os 8C(CO) 22 ( 2) in ca. 15% yield. An X-ray analysis of 2 shows that the carbido-carbon is encapsulated in a trigonal prismatic cavity within the metal core.

Fluxional ligand migrations in triosmium clusters containing 2-pyridylphosphines

The cluster [Os3(CO)10(µ-L)](L = Ph2PC5H4N)(X-ray structure reported), containing the diaxially coordinated 2-pyridyldiphenylphosphine bridge, undergoes rapid transfer of the pyridine between two metal atoms while the phosphorus atom remains firmly coordinated to the third.

Ligand substitution reactions in metal cluster complexes. Evidence for unusually facile metal-metal bond cleavages in the reactions of osmium clusters Os3(CO)11(NCMe) and Os3(CO)10(NCMe)2 with CNCF3 including the isolation and structural characterization of intermediates

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTLigand substitution reactions in metal cluster complexes. Evidence for unusually facile metal-metal bond cleavages in the reactions of osmium clusters Os3(CO)11(NCMe) and Os3(CO)10(NCMe)2 with CNCF3 including the isolation and structural characterization of intermediatesRichard D. Adams, Yun Chi, Darryl D. DesMarteau, Dieter Lentz, Robert Marschall, and Andreas ScherrmannCite this: J. Am. Chem. Soc. 1992, 114, 27, 10822–10826Publication Date (Print):December 1, 1992Publication History Published online1 May 2002Published inissue 1 December 1992https://doi.org/10.1021/ja00053a018RIGHTS & PERMISSIONSArticle Views150Altmetric-Citations20LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (587 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Cyclobutyne: the ligand. The synthesis and molecular structure of osmium cluster Os3(CO)9(.mu.3-.eta.2-C2CH2CH2)(.mu.-SPh)(.mu.-H)

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTCyclobutyne: the ligand. The synthesis and molecular structure of osmium cluster Os3(CO)9(.mu.3-.eta.2-C2CH2CH2)(.mu.-SPh)(.mu.-H)Richard D. Adams, Gong Chen, Xiaosu Qu, Wengan Wu, and John H. YamamotoCite this: J. Am. Chem. Soc. 1992, 114, 27, 10977–10978Publication Date (Print):December 1, 1992Publication History Published online1 May 2002Published inissue 1 December 1992https://doi.org/10.1021/ja00053a053RIGHTS & PERMISSIONSArticle Views130Altmetric-Citations24LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (310 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Synthesis and spectral and X-ray structural studies of novel delocalised di- and tri-phosphazene and their complexes

The di- and tri-phosphazene (CF 3) 2PNPPh 3 ( D) and (C F3) 2PN P(CF 3) 2NPPh3 ( T) can be prepared by stepwise Staudinger reactions with (CF 3) 2PN 3. These reactions demonstrate the feasibility of propagating the active terminal phosphorous. The diphosphazene D has been shown to react with PdCl 2 giving [Pd 2Cl 2D 2] and to displace the acetonitrile molecules from Os 3(CO 11(CH 3CN) and Os 3(CO) 10(CH 3CN) 2 to afford the corresponding clusters Os 3(CO) 11 D and Os 3(CO) 10 D 2. Moreover, reaction with Fe 2(CO) 9 in hexane yields two complexes, namely Fe(CO) 4 D and Fe(CO) 3 D 2. The reaction of the triphosphazene T with Os 3(CO) 11(CH 3CN) is similar to that with the diphosphazene in which the acetonitrile is displaced to afford Os 3(CO) 11P(CF 3) 2NP(CF 3) 2NPPh 3 1. X-ray structures of the ligands and their complexes will be presented. Our findings have established that the highly delocalised electronic structures displayed by the diphosphazene as well as its complexes can be extended to the triphosphazene analogues vis. T and 1 which in turn represents the first examples of a PNPNP non-linear structure containing four-valent as well as five-valent terminal phosphorous atoms. The central phosphorous atom assumes a valency of six.

Ruthenium and osmium cluster with unusual structures induced by the trifluoromethyl isocyanide ligand

Reaction of Ru 3(CO) 11(CH 3CN) and Ru 3(CO) 10(CH 3CN) 2 with CF 3NC yields the cluster compounds, Ru 3(CO) 11(μ 2CNCF 3) and Ru 3(CO) 10(μ 2CNCF 3)2, respectively. In addition, formation of the dinuclear compound Ru 2(CO) 6(μ 2 CNCF 3) 3 is also observed. With Os 3(CO) 11(CH 3CN) and Os 3(CO) 10(CH 3CN) 2, however, derivatives of the hypothetical Os 3(CO) 13 are obtained as primary products by splitting of a metal-metal bond. These open clusters Os 3(CO) 11(μ 2 CNCF 3) 2 and Os 3(CO) 10(CH 3CN)(μ 2CNCF 3) 2 slowly lose carbon monoxide or acetonitrile, forming Os 3(CO) 10(μ 2CNCF 3) 2 and Os 3(CO) 9(CH 3CN)(μ 2 CNCF 3) 2, respectively. The structures of most of these compounds have been established by X-ray crystallography, demonstrating the strong tendency of the trifluoromethyl isocyanide ligand to occupy the bridging position and forcing the clusters to accept unusual structures which are not found with carbonyl ligands or common isocyanides.

Synthesis and spectroscopic characterization of the heteronuclear diphosphine linked cluster Os3(CO)11(Ph2PCH2PPh2)Rh6(CO)15

The synthesis of the heteronuclear diphosphine linked cluster Os3(CO)11(Ph2PCH2PPh2)Rh6(CO)15 is reported. The structure of this compound is discussed on the basis of its IR and 31P NMR spectra.

Halide-promoted carbonylation of the imido ligand in osmium cluster Os3(.mu.3-NPh)(CO)10

The imido cluster Os{sub 3}({mu}{sub 3}-NPh)(CO){sub 10} has been found to react with halides to give the isomeric clusters [PPN][Os{sub 3}({mu}{sub 3}-NPh)({mu}{sub 3}-NPh)({mu}{sub 2}-X)(CO){sub 9}] (7) and [PPN][Os{sub 3}({mu}{sub 3}-NPh)(X)(CO){sub 9}] (8), which have bridging and terminal halide ligands, respectively, with the ratio of the isomers dependent upon the halide used. For chloride, the major isomer is 7, which has been crystallographically shown to have two Os-Os bonds and the chloride ligand bridging two nonbonded Os atoms. For iodide, the major isomer is 8, which has three Os-Os bonds and a terminal iodide ligand. both isomers are present in nearly equal amounts when X = Br. The parent imido cluster Os{sub 3}({mu}{sub 3}-NPh)(CO){sub 10} is inert to carbonylation, but when the isomeric halide-substituted clusters are placed under 1 atm of CO at 22{degree}C, slow carbonylation occurs to form the two new clusters [Os{sub 3}-({eta}{sup 2}-{mu}{sub 3}-PhNCO)({mu}{sub 2}-X)(CO){sub 9}]{sup {minus}}(12) and [Os{sub 3}({eta}{sup 2}-{mu}{sub 2}-PhNCO)({mu}{sub 2}-X)(CO){sub 10}]{sup {minus}}(13), which possess bridging PhNCO ligands resulting from the insertion of CO into the Os-N bond. When left under CO, these clusters further carbonylated to release free PhN{double_bond}C{double_bond}O and form the known compounds [Os{sub 3}(X)(CO){sub 11}]{sup {minus}}. The oxygen atom of the {eta}{sup 2}-{mu}{submore » 2}-PhNCO ligand in 13 can be protonated and alkylated with CF{sub 3}CO{sub 2}H and CF{sub 3}SO{sub 3}CH{sub 3}, respectively, to give the clusters Os{sub 3}({eta}{sup 2}-{mu}{sub 2}-PhNCOR)({mu}{sub 2}-X)(CO){sub 10}(R = H, Me; X = Cl, I), of which the R = Me, X = I derivative has been crystallographically characterized. 27 refs., 6 figs., 10 tabs.« less

Opening of metal carbonyl cluster complexes by ligand addition. Synthesis and structural characterization of osmium cluster Os3(CO)11(.mu.-CNCF3)2, a stabilized derivative of the hypothetical complex Os3(CO)13

Opening of metal carbonyl cluster complexes by ligand addition. Synthesis and structural characterization of osmium cluster Os3(CO)11(.mu.-CNCF3)2, a stabilized derivative of the hypothetical complex Os3(CO)13

Trinuclear benzene clusters of ruthenium and osmium

The activated cluster [Os3(CO)7(µ3-η2:η2:η2-C6H6)(C2H4)(MeCN)] reacts with alkynes RC2R′(R = R′= H, Ph or Me; R = H, R′= Ph; R = Me, R′= Et) to produce the new clusters [Os3(CO)7(η6-C6H6)(µ3-η2-RC2R′)] in which the benzene molecule has migrated to a single osmium atom. In contrast, reaction of the ruthenium cluster [Ru3(CO)9(µ3-η2:η2:η2-C6H6)] with similar alkynes RC2R′(R = R′= H, Ph or Me; R = Ph, R′= H) yields the new clusters [Ru3(CO)7(η6-C6H6)(µ3-η2-RC2R′CO)] in which carbonyl insertion has occurred. The molecular structures of [Os3(CO)7(η6-C6H6)(µ3-η2-C2Me2)] and of [Ru3(CO)7(η6-C6H6)(µ3-η2-PhC2PhCO)] have been established by single-crystal X-ray analysis. The C6H6 ligand is η6-bonded to a single metal atom, while the C2Me2 and the PhC2PhCO ligands lie above the metal triangles and are bonded to the three metal atoms via two σ interactions and one π interaction.

Synthesis and molecular structures of new silylalkyne triosmium clusters

Treatment of the functionalized cluster [Os3(CO)10(MeCN)2] with trimethylsilylacetylene quantitatively affords [Os3(CO)10(HCCSiMe3)]1 which in refluxing heptane undergoes decarbonylation and hydrogen migration yielding [Os3H(CO)9(CCSiMe3)]2 the structure of which was determined by an X-ray study [triclinic, space group P, a= 9.201(2), b= 13.127(2), c= 9.118(7)Å, α= 107.31(3), β= 98.57(3), γ= 93.18(2)°, Z= 2]. Desilylation of 2 affording [Os3H(CO)9(C2H)] takes place either on silica TLC plates or on stirring in hot methanol. The compound [Os3H(CO)10(CCSiMe3)]3 has been prepared through two different routes: (i) reaction of [Os3H(CO)10Cl] with Li[CCSiMe3]; (ii) reaction of [Os3(CO)11(MeCN)] with HCCSiMe3. It has been characterized by X-ray diffraction studies [monoclinic, space group P21/c, a= 13.338(5), b= 9.141(4), c= 18.902(7)Å, β= 109.99(3)°, Z= 4]. On refluxing 3 in heptane, decarbonylation occurs with formation of 2.

Synthesis, structure and reactions of a palladium cluster compound containing bound acetonitrile, [Pd4(µ-SO2)2(µ3-SO2)(MeCN)(PPh3)4

The cluster compound [Pd5(µ-SO2)2(µ3-SO2)2(PPh3)5]1a reacts with acetonitrile to give a tetranuclear compound [Pd4(µ-SO2)2(µ3-SO2)(MeCN)(PPh3)4]2a. Compound 2a has been characterised by a single-crystal X-ray analysis, and shown to have a butterfly arrangement of palladium atoms with Pd–Pd bond distances between 2.754(1) and 2.969(1)Å. Comparison of the solid-state cross-polarisation magic angle spinning 31P-{1H} NMR spectrum with the low-temperature solution 31P-{1H} spectrum indicates that this structure is maintained in solution. However, at room temperature, solutions of 2a revert back to 1a. Like the triangulo-osmium clusters [Os3(CO)11(MeCN)] and [Os3(CO)10(MeCN)2], it has proved possible to replace the labile acetonitrile ligand, and [Pd5(µ-SO2)2(µ3-SO2)2(PMePh2)5]1b can be converted into [Pd4(µ-SO2)2(µ3-SO2)(PMePh2)5]3via the compound [Pd4(µ-SO2)2(µ3-SO2)(MeCN)(PMePh2)4]2b.