Trisubstituted heteropolytungstates as soluble metal oxide analogs. 1. The preparation, characterization, and reactions of organic solvent soluble forms of the silicon-niobium heteropolytungstates Si2W18Nb6O778-, SiW9Nb3O407-, and the SiW9Nb3O407- supported organometallic complex [(C5Me5)Rh.cntdot.SiW9Nb3O40]5-

Finke, Richard G.; Droege, Michael

doi:10.1021/ja00335a086

Cited by 171 publications

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“…[13] This species has proved to be a versatile ligand that can act either as a porphyrin-like tetradentate ligand, [13,14] a bidentate ligand, [15,16] or a bridging ligand. [15,17] In addition it may act as 4 and {Mo(NO)} 3 units. [16,18] The formation of [{Ni(MeOH) 2 } 2 {Mo(NO)} 2 (m 3 -OH) 2 (m-OMe) 4 [16] is reminiscent of the dissolution ± precipitation of oxide supports in the preparation of supported catalysts.…”

Section: (No)]mentioning

confidence: 99%

“…[1] The structural analogy between polyoxometalates and extended oxides was first pointed out by Baker [2] and later expanded by Pope, [1a] Klemperer, [3] Finke [4] and M¸ller. [5] Indeed, the surfaces of many polyanions mimick those of metal oxides, and it is currently thought that the study of transition metal derivatives of polyanions might contribute to the understanding at the molecular level of the different steps of the preparation of heterogeneous metal-oxide-supported catalysts.…”

Section: Introductionmentioning

confidence: 99%

“…This system provides an unique opportunity for probing the basic reactions involved in the preparation of solid oxide-supported heterogeneous catalysts, that is, mobility of transition-metal species at the surface and dissolution ± precipitation of the support. Under nitrogen and in the dark, the reaction of in situ generated fac-{Mn(CO) 3 } species with (nBu 4 N) 2 [Na(MeOH)-{Mo 5 O 13 (OMe) 4 (NO)}] in MeOH yields (nBu 4 N) 2 [Mn(CO) 3 (H 2 O){Mo 5 O 13 -(OMe) 4 (NO)}] at room temperature, while (nBu 4 N) 3 [Na{Mo 5 O 13 (OMe) 4 -(NO)} 2 {Mn(CO) 3 } 2 ] is obtained under reflux. The former transforms into the latter under reflux in methanol in the presence of sodium bromide; this involves the migration of the fac{Mn(CO) 3 } moiety from a basal k 2 O coordination site to a lateral k 3 O site.…”

mentioning

confidence: 99%

“…The former transforms into the latter under reflux in methanol in the presence of sodium bromide; this involves the migration of the fac{Mn(CO) 3 } moiety from a basal k 2 O coordination site to a lateral k 3 O site. Oxidation and decarbonylation of manganese carbonyl species as well as degradation of the oxonitrosyl starting material and reaggregation of oxo-(methoxo)molybdenum fragments occur in non-deareated MeOH, and both (nBu 4 N) 4 2 [Re(CO) 3 -(H 2 O){Mo 5 O 13 (OMe) 4 (NO)}] has also been synthesized. The crystal structures of (nBu 4 N) 2 [Re(CO) 3 (H 2 O){Mo 5 O 13 -(OMe) 4 (NO)}], (nBu 4 N) 3 [Na{Mo 5 O 13 -(OMe) 4 (NO)} 2 {Mn(CO) 3 …”

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Coordination Chemistry of the Soluble Metal Oxide Analogue [Mo₅O₁₃(OCH₃)₄(NO)]³⁻ with Manganese Carbonyl Species

Villanneau

Proust

Robert

et al. 2003

Chemistry A European J

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The reactions of neutral or cationic manganese carbonyl species towards the oxo-nitrosyl complex [Na(MeOH)[Mo(5)O(13)(OCH(3))(4)(NO)]](2-) have been investigated in various conditions. This system provides an unique opportunity for probing the basic reactions involved in the preparation of solid oxide-supported heterogeneous catalysts, that is, mobility of transition-metal species at the surface and dissolution-precipitation of the support. Under nitrogen and in the dark, the reaction of in situ generated fac-[Mn(CO)(3)](+) species with (nBu(4)N)(2)[Na(MeOH)-[Mo(5)O(13)(OMe)(4)(NO)]] in MeOH yields (nBu(4)N)(2)[Mn(CO)(3)(H(2)O)[Mo(5)O(13)(OMe)(4)(NO)]] at room temperature, while (nBu(4)N)(3)[Na[Mo(5)O(13)(OMe)(4)(NO)](2)[Mn(CO)(3)](2)] is obtained under reflux. The former transforms into the latter under reflux in methanol in the presence of sodium bromide; this involves the migration of the fac-[Mn(CO)(3)](+) moiety from a basal kappa(2)O coordination site to a lateral kappa(3)O site. Oxidation and decarbonylation of manganese carbonyl species as well as degradation of the oxonitrosyl starting material and reaggregation of oxo(methoxo)molybdenum fragments occur in non-deareated MeOH, and both (nBu(4)N)(4)[Mn(H(2)O)(2)[Mo(5)O(16)(OMe)(2)](2)[Mn(CO)(3)](2)] and (nBu(4)N)(4)[Mn(H(2)O)(2)[Mo(5)O(13)(OMe)(4)(NO)](2)] as well as (nBu(4)N)(2)[MnBr[Mo(5)O(13)(OMe)(4)(NO)]] have been obtained in this way. The rhenium analogue (nBu(4)N)(2)[Re(CO)(3)(H(2)O)[Mo(5)O(13)(OMe)(4)(NO)]] has also been synthesized. The crystal structures of (nBu(4)N)(2)[Re(CO)(3)(H(2)O)[Mo(5)O(13)(OMe)(4)(NO)]], (nBu(4)N)(3)[Na[Mo(5)O(13)(OMe)(4)(NO)](2)[Mn(CO)(3)](2)], (nBu(4)N)(4)[Mn(H(2)O)(2)[Mo(5)O(16)(OMe)(2)](2)[Mn(CO)(3)](2)], (nBu(4)N)(4)[Mn(H(2)O)(2)[Mo(5)O(13)(OMe)(4)(NO)](2)] and (nBu(4)N)(2)[MnBr[Mo(5)O(13)(OMe)(4)(NO)]] have been determined.

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Section: (No)]mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

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Coordination Chemistry of the Soluble Metal Oxide Analogue [Mo₅O₁₃(OCH₃)₄(NO)]³⁻ with Manganese Carbonyl Species

Villanneau

Proust

Robert

et al. 2003

Chemistry A European J

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“…(Finke and Droege, 1984;Finke et al, 1987;Hill et al, 1990a,b;Droege and Finke, 1991;Weeks et al, 1992;Lyon et al, 1991;Kim et el., 1994). The dextran sulfates were purchased from Sigma Chemical Co. (St Louis, MO).…”

Section: Materials and Experimental Procedures: Chemistrymentioning

confidence: 99%

In vitro Antimyxovirus and Anti-Human Immunodeficiency Virus Activities of Polyoxometalates

Shigeta

Mori

Watanabe

et al. 1995

Antivir Chem Chemother

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Polyoxometalates have been shown to inhibit the replication of retro-, toga-, paramyxo- and herpesviruses. The primary mechanism of the anti-human immunodeficiency virus type 1 (HIV-1) action of polyoxometalates seems to be inhibition of binding of virus to cells and inhibition of syncytium formation. Since myxoviruses and HIV-1 are known to interact with the cytoplasmic membrane by adsorption and penetration of virus and by fusion of infected and uninfected cells, 25 polyoxometalates were examined for anti-ortho-, anti-paramyxovirus and anti-HIV-1 activity in vitro. Of the 25 compounds evaluated, 24 showed antiviral effects against influenza virus A, 11 showed activity against respiratory syncytial virus, six showed activity against measles virus, and 23 were considered effective against HIV-1 at a lower concentration than that producing cytotoxicity. Four polyoxotungstates which had potent inhibitory effects were examined for inhibitory effects against additional ortho- and paramyxoviruses, and proved to have a broad spectrum of antimyxoviral activity. HS-058, the Keggin sandwich compound K10Fe4(H2O)2(PW9O34)2·nH2O, was inhibitory against influenza viruses A and B, respiratory syncytial virus, measles virus, and parainfluenza virus 2, with median effective concentrations of 1.4, 21.8, 7.4, 0.8 and 0.32 μ,M, respectively. However, HS-058 had no effect on parainfluenza virus 3 or mumps virus. The median cytotoxic concentration of HS-058 for Madin-Darby canine kidney (MDCK) and HEp-2 cells was more than 200 μM and that for HMV-2 and Vero cells was about 50 μM. When HS-058 was added at different times after influenza A and respiratory syncytial virus infection, it inhibited binding of the latter but not of the former to cells. However, at higher concentrations, HS-054 and HS-058 inhibited haemolysis of chick erythrocytes by influenza virus and syncytium formation involving respiratory syncytial virus-infected cells and uninfected cells. Four times the median effective antiviral concentration of HS-058 completely inhibited the growth of influenza virus A in MDCK cells when compound was added before virus adsorption. Furthermore, when HS-058 was added after virus adsorption, it inhibited the yield of virus in MDCK cells infected at low but not at high multiplicity of infection.

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Das supramolekulare Tetra-Keggin-Polyoxometallat [Nb4O6(α-Nb3SiW9O40)4]20−

et al. 1999

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Die Selbstanordnung von modularen und aus mehreren Komponenten bestehenden anorganischen Systemen zu gröûeren Strukturen und Materialien mit nützlichen Eigenschaften ist ein intensiv untersuchtes Forschungsfeld. [1] So ist etwa die Bildung von Riesenpolyoxometallaten mit katalytischen, magnetischen und antiviralen Eigenschaften, die zumindest teilweise auf deren Strukturen zurückzuführen sind, von Interesse. [2] Hier beschreiben wir die säureinduzierte Bildung von Nb-O-Nb-Bindungen zwischen Niob-haltigen Polyoxometallat(POM)-Einheiten zum Aufbau supramolekularer Poly-POM-Spezies [3±6] und berichten über die Synthese und Charakterisierung von 1, einem strukturell neuartigen tetrameren Komplex aus Keggin-Ionen. Auûerdem berichten wir über die Stabilität dieses Komplexes unter physiologischen Bedingungen, denn das gut untersuchte Monomer 2 sowie das Dimer 3 [3] gehören zu den stärksten antiviralen und dabei am wenigsten toxischen Verbindungen der mehr als 300 bisher biologisch und pharmakologisch untersuchten POMs. [7±12] [Nb 4 O 6 (a-Nb 3 SiW 9 O 40 ) 4 ] 20À 1 [Nb 3 SiW 9 O 40 ] 7À 2 [Nb 6 Si 2 W 18 O 77 ] 8À 3 Bei der Reaktion von Nb 6 O 19 8À und wäûrigem H 2 O 2 mit festem a-SiW 9 O 34 10À bildet sich 1 in 51 % Ausbeute. Enthalten die zur Synthese verwendeten Keggin-Ionen bereits die drei nötigen Niobatome, ist die Ausbeute an 1 natürlich höher: Man erhält 1 in 81 % Ausbeute, wenn Nb 6 O 19 8À und wäûriges H 2 O 2 mit der festen Triperoxoverbindung a-Cs 6 H-[(NbO 2 ) 3 SiW 9 O 37 ] Cs-4 umgesetzt werden. Beide Reaktionen verlaufen unter stürmischer Sauerstoffentwicklung. Der Versuch, zunächst durch kontrollierte Hydrolyse von Nb(OEt) 5 im Sauren die Nb 4 O 6 8 -Einheit herzustellen, um diese dann Experimentelles Hydrolyse der Ketalgruppe in 1,4-Dioxadispiro[4.0.5.3]tetradecan-7-on (Tabelle 2, Nr. 6): Zu einer Lösung der Spiroverbindung (237 mg, 1.13 mmol) in einem Gemisch aus 3.5 mL Acetonitril und 3.5 mL einer Borat/HCl-Pufferlösung (Merck; pH 8) wird festes CAN (18 mg, 4 Mol-%) gegeben. Die schwach gelbe Lösung wird 1.5 h auf 60 8C erwärmt. Nach dem Abkühlen auf Raumtemperatur werden 10 mL Wasser zugegeben und die organische Phase abgetrennt. Die wäûrige Phase wird noch zweimal mit Dichlormethan extrahiert, und die vereinigten organischen Extrakte werden über MgSO 4 getrocknet. Nach dem Abfiltrieren des Trockenmittels werden die Lösungsmittel unter vermindertem Druck entfernt. Das Rohprodukt wird chromatographisch an Kieselgel gereinigt, wobei das farblose Produkt Spiro[4.5]decan-1,6-dion (144 mg, 86 %) mit EtOAc/ Hexan (3:7; R f 0.58) eluiert wird. 1 H-NMR (CDCl 3 , 300 MHz): d 2.7 (m, 2 H), 2.42 (dt, J 14.1, 5.1 Hz , 1 H), 2.31 (dt, J 8, 1.7 Hz, 2 H), 2.2 ± 1.6 (m, 9 H); 13 C{ 1 H}-NMR (CDCl 3 , 75.5 MHz): d 18. 9, 21.0, 26.6, 33.7, 35.9, 38.4, 39.7, 64.3, 207.9, 215.5; IR (Film): n Ä 1734, 1700 cm À1 ; MS (70 eV): m/z (%): 166 (92) [M ], 167 (100) [M 1].

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Cited by 171 publications

References 1 publication

Coordination Chemistry of the Soluble Metal Oxide Analogue [Mo₅O₁₃(OCH₃)₄(NO)]³⁻ with Manganese Carbonyl Species

Coordination Chemistry of the Soluble Metal Oxide Analogue [Mo₅O₁₃(OCH₃)₄(NO)]³⁻ with Manganese Carbonyl Species

In vitro Antimyxovirus and Anti-Human Immunodeficiency Virus Activities of Polyoxometalates

Das supramolekulare Tetra-Keggin-Polyoxometallat [Nb4O6(α-Nb3SiW9O40)4]20−

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Cited by 171 publications

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Coordination Chemistry of the Soluble Metal Oxide Analogue [Mo5O13(OCH3)4(NO)]3− with Manganese Carbonyl Species

Coordination Chemistry of the Soluble Metal Oxide Analogue [Mo5O13(OCH3)4(NO)]3− with Manganese Carbonyl Species

In vitro Antimyxovirus and Anti-Human Immunodeficiency Virus Activities of Polyoxometalates

Das supramolekulare Tetra-Keggin-Polyoxometallat [Nb4O6(α-Nb3SiW9O40)4]20−

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Coordination Chemistry of the Soluble Metal Oxide Analogue [Mo₅O₁₃(OCH₃)₄(NO)]³⁻ with Manganese Carbonyl Species

Coordination Chemistry of the Soluble Metal Oxide Analogue [Mo₅O₁₃(OCH₃)₄(NO)]³⁻ with Manganese Carbonyl Species