Cluster Complex Os3 Research Articles

The reaction of Os3(CO)12 with triphos {MeC(CH2PPh2)3}: A case of multiple C-P and C-H bond activations

The reaction of Os3(CO)12 with the tripodal ligand 1,1,1-tris(diphenylphosphinomethyl)ethane, triphos, results in the formation of the 48e trinuclear cluster complex Os3[μ-Ph2PCH2C(Me)(CH2PPh)CH2PC6H4](CO)7(η1-Ph). This new complex has been characterized by X-ray crystallography as well as by IR and NMR spectroscopy. The activation of the triphos ligand to yield the novel 9e donor ligand Ph2PCH2C(Me)(CH2PPh)CH2PC6H4 is unprecedented. The triphos ligand does not cap the triangular Os3 face; instead, the three phosphorus atoms are coordinated to only two of the metal atoms with the remaining osmium atom coordinated by an ortho-metalated aryl group. The triphos ligand is also transformed in several ways. Two C–P bonds are cleaved during the reaction, yielding an η1 phenyl ligand in the product and free benzene. The bonding in 1 has been examined by electronic structure calculations.

Multicenter transformations of the methyl ligand in CH3Os3Au carbonyl cluster complexes: Synthesis, characterization and DFT analyses

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-OCCH3) (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.

Addition of Pt(PBut3) to Osmium−Tin Cluster Complexes

The reactions of the osmium-tin cluster complexes Os3(CO)12(mu3-SnPh)Ph, 9, and Os4(CO)16(mu4-Sn), 10, with Pt(PBut3)2 have been investigated. Two products, PtOs3(CO)12(Ph)(PBut3)(mu3-SnPh), 11, and Pt2Os3(CO)12(mu2-Ph)(PBut3)2(mu3-SnPh), 12, were obtained from the reaction of 9 with Pt(PBut3)2. These are mono- and bis-Pt(PBut3) adducts of 9 formed by the addition of a Pt(PBut3) group to the Os-Os bond in 11 and the Os-Os bond and Os-C bond to the sigma-bonded phenyl group in 12. A PBut3 derivative of 11, Os2(CO)8(mu3-SnPh)Os(CO)3(PBut3)Ph, 13, was obtained by treating 12 with PBut3. The reaction of 10 with Pt(PBut3)2 provided the bis-Pt(PBut3) adduct Os4(CO)16[Pt(PBut3)]2(mu4-Sn), 14, that was formed by the addition of a Pt(PBut3) group across the Os-Os bond of both Os2(CO)8 groups in 10. All four new compounds 11-14 were characterized by single-crystal X-ray diffraction analysis.

En Route to the Formation of High-Efficiency, Osmium(II)-Based Phosphorescent Materials

Triosmium cluster complexes [Os3(CO)8(fppz)2] (2a) and [Os3(CO)8(fptz)2] (2b) bearing two 2-pyridyl azolate ligands were synthesized in an attempt to establish the reaction mechanism that gives rise to the blue-emitting phosphorescent complexes [Os(CO)2(fppz)2] (1a) and [Os(CO)2(fptz)2] (1b) [(fppz)H = 3-(trifluoromethyl)-5-(2-pyridyl)pyrazole; (fptz)H = 3-(trifluoromethyl)-5-(2-pyridyl)triazole]. X-ray structural analysis of 2b showed an open triangular metal framework incorporating multisite-coordinated 2-pyridyltriazolate ligands. Treatment of 2 with the respective 2-pyridylazolate ligand led to the formation of blue-emitting complex 1b, confirming their intermediacy, while the reaction of 2b with phosphine ligand PPh2Me afforded two hitherto novel hydride complexes 3 and 4, for which the reversible interconversion was clearly established at higher temperatures (> 180 degrees C). The single-crystal X-ray diffraction analyses of 3 and 4 confirmed their monometallic and isomeric nature, together with the coordination of two phosphine ligands located in the trans-disposition and one CO and one hydride located opposite to the pyridyl triazolate chelate. Subtle differences in photophysical properties were examined for isomers 3 and 4 on the basis of steady state absorption and emission, the relaxation dynamics, and temperature-dependent luminescent studies. The results, in combination with time-dependent density function theory (TDDFT) calculations, provide fundamental insights into the future design and preparation of highly efficient phosphorescent emitters.

Cluster Fragmentation and Facile Cleavage of Phenyl Groups from the SnPh3Ligand in Reactions of Os3(CO)11(SnPh3)(μ-H) with CO and HSnPh3

Two new cluster complexes, Os3(CO)12(Ph)(μ3-SnPh), 8 (35% yield), and Os4(CO)16(μ4-Sn), 9 (10% yield), were formed when the complex Os3(CO)11(SnPh3)(μ-H), 6, was heated to reflux in toluene solvent under a CO atmosphere. Compound 8 was transformed to 9 in 28% yield when a solution in octane solvent was heated to reflux under a CO atmosphere. Biphenyl was a coproduct in this reaction. Compound 8 contains three osmium atoms with a triply bridging SnPh group. The triosmium cluster has opened and there is only one Os−Os bond between the three osmium atoms. Compound 9 contains two Os2(CO)8 groups held together by a central quadruply bridging tin atom, giving an overall bow-tie structure for the five metal atoms. Two other new compounds, Os2(CO)6(μ-SnPh2)2(SnPh3)2, 10, and HOs(CO)4(SnPh3), 11, were formed in 51% and 20% yields, respectively, from the reaction of 6 with HSnPh3. Compound 10 contains only two osmium atoms linked by an Os−Os bond and two bridging SnPh2 ligands. Each osmium atom also contains one te...

A New Tris(diphenylstannylene)triosmium Carbonyl Cluster Complex and Its Reactions with Pt(PBut3)2and Pt(PPh3)4

The reaction of Os3(CO)12 with Ph3SnH yielded the bimetallic Os−Sn cluster complexes Os3(CO)11(SnPh3)(μ-H) (16) and Os3(CO)9(μ-SnPh2)3 (17) in 20 and 21% yields, respectively. Compound 16 consists of an Os3 triangle with a terminal SnPh3 group on one of the Os atoms and a bridging hydrido ligand across one of the Os−Os bonds. Compound 17 consists of a central Os3 triangle with SnPh2 groups bridging each of the three Os−Os bonds. Pt(PBut3)2 reacts with compound 17 to afford Os3(CO)9[Pt(PBut3)](μ-SnPh2)3 (18), a Pt(PBut3) adduct of 17, in 29% yield by adding a Pt(PBut3) group across one of the Os−Sn bonds. The osmium and tin atoms lie in a plane, while the Pt(PBut3) group is displaced slightly out of that plane. Pt(PPh3)4 reacts with 17 to give the cluster complex Os3(CO)9[Pt(Ph)(PPh3)2](μ-SnPh2)2(μ3-SnPh) (19) in 21% yield by insertion of a Pt(PPh3)2 into one of the Sn−C bonds to one of the phenyl groups. The osmium and tin atoms are coplanar, and there is a Pt(Ph)(PPh3)2 group terminally bonded to one of ...

Unusually High Performance Photovoltaic Cell Based on a [60]Fullerene Metal Cluster−Porphyrin Dyad SAM on an ITO Electrode

A self-assembled monolayer (SAM) of a C60-triosmium cluster complex Os3(CO)7(CNR)(CNR')(mu3-eta2:eta2:eta2-C60) (ZnP-C60; R = (CH2)3Si(OEt)3, R' = ZnP) on an ITO surface exhibits ideal electrochemical responses as well as remarkable enhancement of the photocurrent generation. The diazabicyclooctane (DABCO) binding (ZnP)-C60/ITO/AsA/Pt cell shows the highest photocurrent generation quantum yield (19.5%) ever reported for the molecular photovoltaic cells based on the covalently linked donor-acceptor dyad structures. The high efficiency in photocurrent generation is ascribed to an efficient electron transfer from photoexcited porphyrin to fullerene, revealed by fluorescence lifetime measurements and transient absorption decay profiles. These results provide valuable information on the new strategy for the construction of molecular photonic devices and artificial photosynthetic systems on ITO electrodes.

The first observation of four-electron reduction in [60]fullerene-metal cluster self-assembled monolayers (SAMs).

Self-assembled monolayers (SAMs) of a mu 3-eta 2:eta 2:eta 2-C60 triosmium cluster complex Os3(CO)8(CN(CH2)3Si(OEt)3)(mu 3-eta 2:eta 2:eta 2-C60) (2) on ITO or Au surface exhibit ideal, well-defined electrochemical responses and remarkable electrochemical stability being reducible up to tetranionic species in their cyclic voltammograms.

New Triosmium Complexes Containing a Partially Hydrogenated Bis(ferrocenyl)butadiyne Ligand. Their Structures and Electrochemical Responses

The reaction of Os3(CO)10(μ3-FcC4Fc) (3) (Fc = C5H5FeC5H4) with water in thf solvent at reflux yielded three new cluster complexes: Os3(CO)9(μ3-η3-E-FcC3CHFc)(μ-H) (4) (54%), Os3(CO)9(μ3-η3-Z-FcC3...

Synthesis and Characterization of η2-C60 and μ3-η2,η2,η2-C60 Triosmium Cluster Complexes

Various η2-C60 and μ3-η2,η2,η2-C60 triosmium carbonyl cluster complexes Os3(CO)11(η2-C60) (1), Os3(CO)10(NCMe)(η2-C60) (2), Os3(CO)10(PPh3)(η2-C60) (3), Os3(CO)9(PR3)2(η2-C60) (4, R = Ph; 5, R = Me), Os3(CO)9(μ3-η2,η2,η2-C60) (6), and Os3(CO)8(PMe3)(μ3-η2,η2,η2-C60) (7) have been isolated as crystalline solids and characterized by spectroscopic (IR, MS, and 1H, 31P, and 13C NMR) and analytical data. The molecular structure of complex 1 has been determined by a single-crystal X-ray diffraction study. The structure of 1 is derived from that of Os3(CO)12 by replacing an equatorial carbonyl ligand with an η2-C60 ligand coordinated through a 6−6 ring fusion. The structural assignment of 2−7 is made on the basis of spectroscopic results. Compound 2 exists as two isomers in solution in a ratio of 2:1 (2a:2b). VT 13C NMR spectra of 2a and 5 indicate that both complexes undergo similar fluxional processes of restricted equilibration of in-plane equatorial C60 and carbonyl ligands via a triply bridged intermediate with identical values of ΔGc⧧ = 12.7 ± 0.1 kcal/mol. Thermolysis of 2 in refluxing chlorobenzene affords Os3(CO)9(μ3-η2,η2,η2-C60) (6) in 23% yield, which can be alternatively prepared in 32% yield from the reaction of Os3(CO)10(NCMe)2 (2 equiv) and C60 (1 equiv). Decarbonylation of 6 with Me3NO/MeCN reagent in the presence of excess PMe3 gives Os3(CO)8(PMe3)(μ3-η2,η2,η2-C60) (7) in a quantitative yield. VT 13C NMR spectra of both 6 and 7 reveal a localized-3-fold rotation of carbonyl and phosphine ligands on each osmium center.

The synthesis and structural characterization of Os3(CO)8[Si(OMe)3][?-PMe2(C6H4](?-H)2: An unusual unsaturated triosmium cluster complex

The reaction of Os3(CO)10(NCMe)[Si(OMe)3](μ-H),1, with PMe2Ph yielded the new complex Os3(CO)10(PMe2Ph)[Si(OMe)3](μ-H),2 by substitution of the MeCn ligand with the phosphine ligand. When heated to 125°C compound2 was decarbonylated and transformed into the new unsaturated cluster complex Os3(CO)8[μ-PMe2(C6H4)][Si(OMe)3](μ-H)2,3 in 54% yield. Compound3 was characterized by a single crystal X-ray diffraction analysis, osmium bonds. The phenyl ring of the phosphine ligand has undergoneortho-metallation by a neighboring metal atom. A terminally coordinated Si(OMe)3 ligand is coordinated to the third osmium atom. The cluster is unsaturated by the amount of 2 electrons, and there is an open coordination site on the siloxyl substituted osmium atom that is partially filled by a weak interaction with one of the π-bonds of theortho-metalled phenyl ring. Complex3 reacts with CO at 1 atm to reform compound2 in 85% yield in 5 h at 40°C. Crystal Data: for3: space group = P21/n,a = 9.911(2) A,b = 18.451(6) A,c = 14.872(2) A,β = 95.64(2)°,Z = 4, 1994 reflections,R = 0.028.

Promotion of ring-opening nucleophilic addition to thietane ligands by the bridging coordination of the sulfur atom in the osmium cluster complexes Os3(CO)10[.mu.-[cyclic]SCH2CMe2CH2] and Os3(CO)10[.mu.-trans-[cyclic]SC(H)MeCH2C(H)Me

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTPromotion of ring-opening nucleophilic addition to thietane ligands by the bridging coordination of the sulfur atom in the osmium cluster complexes Os3(CO)10[.mu.-[cyclic]SCH2CMe2CH2] and Os3(CO)10[.mu.-trans-[cyclic]SC(H)MeCH2C(H)Me]Richard D. Adams and Michael P. PompeoCite this: Organometallics 1992, 11, 4, 1460–1465Publication Date (Print):April 1, 1992Publication History Published online1 May 2002Published inissue 1 April 1992https://doi.org/10.1021/om00040a014RIGHTS & PERMISSIONSArticle Views41Altmetric-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 (766 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Clusters containing carbene ligands. 14. Further studies of the reactivity of the carbene centers in the dicarbene cluster complex Os3(CO)9[.mu.3-C(Et)N(Me)CH](.mu.-H)2 with diphenylacetylene

Six products were obtained from the reaction of Os{sub 3}(CO){sub 9}[{mu}{sub 3}-C(Et)N(Me)CH]({mu}-H){sub 2}: (1) with PhC{sub 2}Ph at 125 {degrees}C. They have been identified as the two previously reported compounds Os{sub 3}(CO){sub 8}[{mu}{sub 3}-{eta}{sup 2}-C(H)N-(Me)C(Et)][{eta}{sup 2}-CPhC(H)Ph]({mu}-H) (2) (3%) and Os{sub 3}(CO){sub 8}({mu}{sub 3}-C[C(Ph)CH(Ph)]N(Me)C(Et))({mu}-H){sub 2} (3) (39%) and four new compounds Os{sub 3}(CO){sub 8}({mu}-{eta}{sup 3}-C[N(Me)C(Et)]C(Ph)C(Ph))({mu}-H) (4) (4%), Os{sub 3}(CO){sub 8}({mu}{sub 3}-CEt)[{mu}-N(Me)C(H)C(Ph)CPh] (5) (6%), Os{sub 3}(CO){sub 8}[C(Et)N(Me)CH{sub 2}][{mu}{sub 3}-C(Ph)C(Ph)]({mu}-H) (6) (3%), and Os{sub 3}-(CO){sub 7}({mu}{sub 3}-C[C(Ph)CH(Ph)]N(Me)C(Et))[{eta}{sup 2}-C(Ph)C(H)Ph]({mu}-H) (7) (3%). Compounds 4-7 were characterized by IR, {sup 1}H NMR, and single-crystal X-ray diffraction analyses. 19 refs., 5 figs., 17 tabs.

Metal cluster-induced electrophilicity of arenes

Hydride or carbanion attack on the triosmium cluster complexes [Os3(CO)9(µ3-η2:η2:η2-C6H5R)], R = H or Me, proceeds highly regio- and stereo-selectively at the face-capping arene ligands. The exo-addition products are anionic, triply bridging cyclohexadienyl complexes [Os3(CO)9(µ3-η2:σ:η2- C6H5RR′)]–, R′= H, Me, or Ph, that yield neutral compounds [Os3(CO)9(µ-E)(µ3-η2:σ:η2-C6H5RR′)] on reaction with electrophiles E = H+ or Au(PEt3)+.

Clusters containing carbene ligands. The unusual synthesis, coordination, and reactivity of a bridging (dimetalliomethyl)(diethylamino)carbene ligand in the cluster complex Os3(CO)9[.mu.3-HCC(NEt2)](.mu.-H)2

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTClusters containing carbene ligands. The unusual synthesis, coordination, and reactivity of a bridging (dimetalliomethyl)(diethylamino)carbene ligand in the cluster complex Os3(CO)9[.mu.3-HCC(NEt2)](.mu.-H)2Richard D. Adams and James T. TannerCite this: Organometallics 1988, 7, 10, 2241–2243Publication Date (Print):October 1, 1988Publication History Published online1 May 2002Published inissue 1 October 1988https://doi.org/10.1021/om00100a031RIGHTS & PERMISSIONSArticle Views43Altmetric-Citations19LEARN 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 (429 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts