Synthesis, molecular dynamics, and reactivity of mixed-metal clusters
Various mixed-metal tetranuclear clusters have been prepared by the combination of a carbonylmetalate with a closed metal carbonyl trimer. The cluster included Fe, Ru, Os, and Co in various combinations. Since transition-metal cluster compounds are currently being examined as catalysts for a variety...
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| Veröffentlicht in: | Acc. Chem. Res.; (United States) 1980-12, Vol.13 (12), p.469-476 |
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| creator | Geoffroy, Gregory L |
| description | Various mixed-metal tetranuclear clusters have been prepared by the combination of a carbonylmetalate with a closed metal carbonyl trimer. The cluster included Fe, Ru, Os, and Co in various combinations. Since transition-metal cluster compounds are currently being examined as catalysts for a variety of reactions involving CO, the reactions of mixed-metal clusters with CO were examined. It was found that most of the clusters studied fragmented in the presence of CO under mild conditions. Results of kinetic studies of the reactions are presented. The cluster compounds were found to react with tertiary phosphines and phosphites to yield mono- and di-substituted clusters. Isomeric products were also found to result from the reaction of the cluster compounds with internal alkynes with hydrogen evolved during the reaction. Results of studies of the molecular dynamics of the series of clusters H/sub 2/FeRu/sub 3/(CO)/sub 13/, H/sub 2/FeRu/sub 2/Os(CO)/sub 13/ and H/sub 2/FeRuOs/sub 2/(CO)/sub 13/ in which Ru is progressively replaced by Os are reported, and several different fluxional processes were observed. The /sup 13/C NMR spectra of these carbonyls are reported. (BLM) |
| doi_str_mv | 10.1021/ar50156a006 |
| format | Article |
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The cluster included Fe, Ru, Os, and Co in various combinations. Since transition-metal cluster compounds are currently being examined as catalysts for a variety of reactions involving CO, the reactions of mixed-metal clusters with CO were examined. It was found that most of the clusters studied fragmented in the presence of CO under mild conditions. Results of kinetic studies of the reactions are presented. The cluster compounds were found to react with tertiary phosphines and phosphites to yield mono- and di-substituted clusters. Isomeric products were also found to result from the reaction of the cluster compounds with internal alkynes with hydrogen evolved during the reaction. Results of studies of the molecular dynamics of the series of clusters H/sub 2/FeRu/sub 3/(CO)/sub 13/, H/sub 2/FeRu/sub 2/Os(CO)/sub 13/ and H/sub 2/FeRuOs/sub 2/(CO)/sub 13/ in which Ru is progressively replaced by Os are reported, and several different fluxional processes were observed. The /sup 13/C NMR spectra of these carbonyls are reported. 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Res.; (United States), 1980-12, Vol.13 (12), p.469-476</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a328t-2e1fdbac000c29369371f09d8f2b22c6403e8296abd70802556dc52be42b432a3</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ar50156a006$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ar50156a006$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,885,2763,27074,27922,27923,56736,56786</link.rule.ids><backlink>$$Uhttps://www.osti.gov/biblio/6480048$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Geoffroy, Gregory L</creatorcontrib><creatorcontrib>Pennsylvania State Univ., University Park</creatorcontrib><title>Synthesis, molecular dynamics, and reactivity of mixed-metal clusters</title><title>Acc. Chem. Res.; (United States)</title><addtitle>Acc. Chem. Res</addtitle><description>Various mixed-metal tetranuclear clusters have been prepared by the combination of a carbonylmetalate with a closed metal carbonyl trimer. The cluster included Fe, Ru, Os, and Co in various combinations. Since transition-metal cluster compounds are currently being examined as catalysts for a variety of reactions involving CO, the reactions of mixed-metal clusters with CO were examined. It was found that most of the clusters studied fragmented in the presence of CO under mild conditions. Results of kinetic studies of the reactions are presented. The cluster compounds were found to react with tertiary phosphines and phosphites to yield mono- and di-substituted clusters. Isomeric products were also found to result from the reaction of the cluster compounds with internal alkynes with hydrogen evolved during the reaction. Results of studies of the molecular dynamics of the series of clusters H/sub 2/FeRu/sub 3/(CO)/sub 13/, H/sub 2/FeRu/sub 2/Os(CO)/sub 13/ and H/sub 2/FeRuOs/sub 2/(CO)/sub 13/ in which Ru is progressively replaced by Os are reported, and several different fluxional processes were observed. The /sup 13/C NMR spectra of these carbonyls are reported. (BLM)</description><subject>08 HYDROGEN</subject><subject>080100 - Hydrogen- Production</subject><subject>090121 - Hydrocarbon Fuels- Chemical Synthesis- (1976-1989)</subject><subject>10 SYNTHETIC FUELS</subject><subject>400201 - Chemical & Physicochemical Properties</subject><subject>400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)</subject><subject>ALKYNES</subject><subject>CARBON COMPOUNDS</subject><subject>CARBON MONOXIDE</subject><subject>CARBON OXIDES</subject><subject>CARBONYLS</subject><subject>CATALYSIS</subject><subject>CATALYTIC EFFECTS</subject><subject>CHALCOGENIDES</subject><subject>CHEMICAL PREPARATION</subject><subject>CHEMICAL REACTIONS</subject><subject>COBALT COMPLEXES</subject><subject>COMPLEXES</subject><subject>DATA</subject><subject>EXPERIMENTAL DATA</subject><subject>HYDROCARBONS</subject><subject>HYDROGEN PRODUCTION</subject><subject>INFORMATION</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>IRON COMPLEXES</subject><subject>KINETICS</subject><subject>NUMERICAL DATA</subject><subject>ORGANIC COMPOUNDS</subject><subject>OSMIUM COMPLEXES</subject><subject>OXIDES</subject><subject>OXYGEN COMPOUNDS</subject><subject>PHOSPHINES</subject><subject>PHOSPHORUS COMPOUNDS</subject><subject>REACTION KINETICS</subject><subject>RUTHENIUM COMPLEXES</subject><subject>SYNTHESIS</subject><subject>TABLES</subject><subject>TRANSITION ELEMENT COMPLEXES</subject><issn>0001-4842</issn><issn>1520-4898</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1980</creationdate><recordtype>article</recordtype><recordid>eNptkE9LxDAQxYMouK6e_ALFiwetTqZp2h51WVdhRWHXc0jTlM3aP5JkZfvtjVTEg6eZefx4w3uEnFO4oYD0VtoUaMolAD8gE5oixCwv8kMyAQAadobH5MS5bTiR8WxC5quh8xvtjLuO2r7RatdIG1VDJ1ujgia7KrJaKm8-jR-ivo5as9dV3Govm0g1O-e1dafkqJaN02c_c0reHubr2WO8fFk8ze6WsUww9zFqWlelVOG7wiLhRZLRGooqr7FEVJxBonMsuCyrDHLANOWVSrHUDEuWoEym5GL07Z03winjtdqovuu08oKzHIDlAboaIWV756yuxYc1rbSDoCC-axJ_agp0PNImJNn_otK-C54lWSrWryvxvKAIxf1CZIG_HHmpnNj2O9uFwP86fwFey3To</recordid><startdate>19801201</startdate><enddate>19801201</enddate><creator>Geoffroy, Gregory L</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>19801201</creationdate><title>Synthesis, molecular dynamics, and reactivity of mixed-metal clusters</title><author>Geoffroy, Gregory L</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a328t-2e1fdbac000c29369371f09d8f2b22c6403e8296abd70802556dc52be42b432a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1980</creationdate><topic>08 HYDROGEN</topic><topic>080100 - Hydrogen- Production</topic><topic>090121 - Hydrocarbon Fuels- Chemical Synthesis- (1976-1989)</topic><topic>10 SYNTHETIC FUELS</topic><topic>400201 - Chemical & Physicochemical Properties</topic><topic>400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)</topic><topic>ALKYNES</topic><topic>CARBON COMPOUNDS</topic><topic>CARBON MONOXIDE</topic><topic>CARBON OXIDES</topic><topic>CARBONYLS</topic><topic>CATALYSIS</topic><topic>CATALYTIC EFFECTS</topic><topic>CHALCOGENIDES</topic><topic>CHEMICAL PREPARATION</topic><topic>CHEMICAL REACTIONS</topic><topic>COBALT COMPLEXES</topic><topic>COMPLEXES</topic><topic>DATA</topic><topic>EXPERIMENTAL DATA</topic><topic>HYDROCARBONS</topic><topic>HYDROGEN PRODUCTION</topic><topic>INFORMATION</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>IRON COMPLEXES</topic><topic>KINETICS</topic><topic>NUMERICAL DATA</topic><topic>ORGANIC COMPOUNDS</topic><topic>OSMIUM COMPLEXES</topic><topic>OXIDES</topic><topic>OXYGEN COMPOUNDS</topic><topic>PHOSPHINES</topic><topic>PHOSPHORUS COMPOUNDS</topic><topic>REACTION KINETICS</topic><topic>RUTHENIUM COMPLEXES</topic><topic>SYNTHESIS</topic><topic>TABLES</topic><topic>TRANSITION ELEMENT COMPLEXES</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Geoffroy, Gregory L</creatorcontrib><creatorcontrib>Pennsylvania State Univ., University Park</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>Acc. Chem. Res.; (United States)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Geoffroy, Gregory L</au><aucorp>Pennsylvania State Univ., University Park</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis, molecular dynamics, and reactivity of mixed-metal clusters</atitle><jtitle>Acc. Chem. Res.; (United States)</jtitle><addtitle>Acc. Chem. Res</addtitle><date>1980-12-01</date><risdate>1980</risdate><volume>13</volume><issue>12</issue><spage>469</spage><epage>476</epage><pages>469-476</pages><issn>0001-4842</issn><eissn>1520-4898</eissn><abstract>Various mixed-metal tetranuclear clusters have been prepared by the combination of a carbonylmetalate with a closed metal carbonyl trimer. The cluster included Fe, Ru, Os, and Co in various combinations. Since transition-metal cluster compounds are currently being examined as catalysts for a variety of reactions involving CO, the reactions of mixed-metal clusters with CO were examined. It was found that most of the clusters studied fragmented in the presence of CO under mild conditions. Results of kinetic studies of the reactions are presented. The cluster compounds were found to react with tertiary phosphines and phosphites to yield mono- and di-substituted clusters. Isomeric products were also found to result from the reaction of the cluster compounds with internal alkynes with hydrogen evolved during the reaction. Results of studies of the molecular dynamics of the series of clusters H/sub 2/FeRu/sub 3/(CO)/sub 13/, H/sub 2/FeRu/sub 2/Os(CO)/sub 13/ and H/sub 2/FeRuOs/sub 2/(CO)/sub 13/ in which Ru is progressively replaced by Os are reported, and several different fluxional processes were observed. The /sup 13/C NMR spectra of these carbonyls are reported. (BLM)</abstract><cop>United States</cop><pub>American Chemical Society</pub><doi>10.1021/ar50156a006</doi><tpages>8</tpages></addata></record> |
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| subjects | 08 HYDROGEN 080100 - Hydrogen- Production 090121 - Hydrocarbon Fuels- Chemical Synthesis- (1976-1989) 10 SYNTHETIC FUELS 400201 - Chemical & Physicochemical Properties 400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987) ALKYNES CARBON COMPOUNDS CARBON MONOXIDE CARBON OXIDES CARBONYLS CATALYSIS CATALYTIC EFFECTS CHALCOGENIDES CHEMICAL PREPARATION CHEMICAL REACTIONS COBALT COMPLEXES COMPLEXES DATA EXPERIMENTAL DATA HYDROCARBONS HYDROGEN PRODUCTION INFORMATION INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY IRON COMPLEXES KINETICS NUMERICAL DATA ORGANIC COMPOUNDS OSMIUM COMPLEXES OXIDES OXYGEN COMPOUNDS PHOSPHINES PHOSPHORUS COMPOUNDS REACTION KINETICS RUTHENIUM COMPLEXES SYNTHESIS TABLES TRANSITION ELEMENT COMPLEXES |
| title | Synthesis, molecular dynamics, and reactivity of mixed-metal clusters |
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