Synthesis and Interconversion of Some Small Ruthenaboranes: Reaction of a Ruthenium Borohydride with Pentaborane(9) to Form Larger Ruthenaboranes

Synthesis and Interconversion of Some Small Ruthenaboranes: Reaction of a Ruthenium Borohydride with Pentaborane(9) to Form Larger Ruthenaboranes

A number of ruthenaborane clusters have been prepared containing the {(η-C5Me5)Ru(PMe3)} fragment. Reaction of [(η-C5Me5)Ru(PMe3)H3] with 1 equiv of BH3·thf gives [(η-C5Me5)Ru(PMe3)BH4] (1), which reacts further with another equivalent of BH3·thf to give [(η-C5Me5)Ru(PMe3)B2H7] (2) in nearly quantit...

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Veröffentlicht in:Organometallics 2007-07, Vol.26 (16), p.4031-4037
Hauptverfasser: Green, Malcolm L. H, Leach, John B, Kelland, Malcolm A
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creator Green, Malcolm L. H
Leach, John B
Kelland, Malcolm A
description A number of ruthenaborane clusters have been prepared containing the {(η-C5Me5)Ru(PMe3)} fragment. Reaction of [(η-C5Me5)Ru(PMe3)H3] with 1 equiv of BH3·thf gives [(η-C5Me5)Ru(PMe3)BH4] (1), which reacts further with another equivalent of BH3·thf to give [(η-C5Me5)Ru(PMe3)B2H7] (2) in nearly quantitative yield. Thermolysis of 2 in solution at 60 °C gives a mixture of 1, arachno-2-[(η-C5Me5)Ru(PMe3)B3H8] (3), and arachno-1-[(η-C5Me5)Ru(PMe3)B3H8] (4). Thermolysis of the wing isomer 3 in solution at 100 °C gives 100% conversion to the hinge isomer 4. Thermolysis in a solution of arachno-3-[(η-C5Me5)Ru(PMe3)B4H9] also gives 4 and 1. The borohydride 1 reacts with pentaborane(9) to give four ruthenaborane clusters, compound 3, nido-2-[(η-C5Me5)RuB5H10] (5), arachno-2-[(η-C5Me5)Ru(PMe3)B5H8] (6), and arachno-3-[(η-C5Me5)Ru(PMe3)B4H9] (7). Thermolysis of 5 in solution gives nido-1-[(η-C5Me5)RuB5H10] (8) in good yield. Compound 5 deprotonates cleanly at the unique basal B−H−B bridge on reaction with KH in thf to form nido-2-[(η-C5Me5)RuB5H9 -][K+] (9). Compound 8 deprotonates cleanly at a B−H−B bridge on reaction with KH in thf to form fluxional nido-1-[(η-C5Me5)RuB5H9 -][K+] (10). The X-ray crystal structure of 3 is reported.
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H ; Leach, John B ; Kelland, Malcolm A</creator><creatorcontrib>Green, Malcolm L. H ; Leach, John B ; Kelland, Malcolm A</creatorcontrib><description>A number of ruthenaborane clusters have been prepared containing the {(η-C5Me5)Ru(PMe3)} fragment. Reaction of [(η-C5Me5)Ru(PMe3)H3] with 1 equiv of BH3·thf gives [(η-C5Me5)Ru(PMe3)BH4] (1), which reacts further with another equivalent of BH3·thf to give [(η-C5Me5)Ru(PMe3)B2H7] (2) in nearly quantitative yield. Thermolysis of 2 in solution at 60 °C gives a mixture of 1, arachno-2-[(η-C5Me5)Ru(PMe3)B3H8] (3), and arachno-1-[(η-C5Me5)Ru(PMe3)B3H8] (4). Thermolysis of the wing isomer 3 in solution at 100 °C gives 100% conversion to the hinge isomer 4. Thermolysis in a solution of arachno-3-[(η-C5Me5)Ru(PMe3)B4H9] also gives 4 and 1. The borohydride 1 reacts with pentaborane(9) to give four ruthenaborane clusters, compound 3, nido-2-[(η-C5Me5)RuB5H10] (5), arachno-2-[(η-C5Me5)Ru(PMe3)B5H8] (6), and arachno-3-[(η-C5Me5)Ru(PMe3)B4H9] (7). Thermolysis of 5 in solution gives nido-1-[(η-C5Me5)RuB5H10] (8) in good yield. Compound 5 deprotonates cleanly at the unique basal B−H−B bridge on reaction with KH in thf to form nido-2-[(η-C5Me5)RuB5H9 -][K+] (9). Compound 8 deprotonates cleanly at a B−H−B bridge on reaction with KH in thf to form fluxional nido-1-[(η-C5Me5)RuB5H9 -][K+] (10). 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H</creatorcontrib><creatorcontrib>Leach, John B</creatorcontrib><creatorcontrib>Kelland, Malcolm A</creatorcontrib><title>Synthesis and Interconversion of Some Small Ruthenaboranes: Reaction of a Ruthenium Borohydride with Pentaborane(9) to Form Larger Ruthenaboranes</title><title>Organometallics</title><addtitle>Organometallics</addtitle><description>A number of ruthenaborane clusters have been prepared containing the {(η-C5Me5)Ru(PMe3)} fragment. Reaction of [(η-C5Me5)Ru(PMe3)H3] with 1 equiv of BH3·thf gives [(η-C5Me5)Ru(PMe3)BH4] (1), which reacts further with another equivalent of BH3·thf to give [(η-C5Me5)Ru(PMe3)B2H7] (2) in nearly quantitative yield. Thermolysis of 2 in solution at 60 °C gives a mixture of 1, arachno-2-[(η-C5Me5)Ru(PMe3)B3H8] (3), and arachno-1-[(η-C5Me5)Ru(PMe3)B3H8] (4). Thermolysis of the wing isomer 3 in solution at 100 °C gives 100% conversion to the hinge isomer 4. Thermolysis in a solution of arachno-3-[(η-C5Me5)Ru(PMe3)B4H9] also gives 4 and 1. The borohydride 1 reacts with pentaborane(9) to give four ruthenaborane clusters, compound 3, nido-2-[(η-C5Me5)RuB5H10] (5), arachno-2-[(η-C5Me5)Ru(PMe3)B5H8] (6), and arachno-3-[(η-C5Me5)Ru(PMe3)B4H9] (7). Thermolysis of 5 in solution gives nido-1-[(η-C5Me5)RuB5H10] (8) in good yield. Compound 5 deprotonates cleanly at the unique basal B−H−B bridge on reaction with KH in thf to form nido-2-[(η-C5Me5)RuB5H9 -][K+] (9). Compound 8 deprotonates cleanly at a B−H−B bridge on reaction with KH in thf to form fluxional nido-1-[(η-C5Me5)RuB5H9 -][K+] (10). 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H</creator><creator>Leach, John B</creator><creator>Kelland, Malcolm A</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20070730</creationdate><title>Synthesis and Interconversion of Some Small Ruthenaboranes: Reaction of a Ruthenium Borohydride with Pentaborane(9) to Form Larger Ruthenaboranes</title><author>Green, Malcolm L. H ; Leach, John B ; Kelland, Malcolm A</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a297t-dc999f371958c57ffc21e920fc05dd07781119a3432d73ffbeeb772986394e8b3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2007</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Green, Malcolm L. H</creatorcontrib><creatorcontrib>Leach, John B</creatorcontrib><creatorcontrib>Kelland, Malcolm A</creatorcontrib><collection>Istex</collection><collection>CrossRef</collection><jtitle>Organometallics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Green, Malcolm L. H</au><au>Leach, John B</au><au>Kelland, Malcolm A</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis and Interconversion of Some Small Ruthenaboranes: Reaction of a Ruthenium Borohydride with Pentaborane(9) to Form Larger Ruthenaboranes</atitle><jtitle>Organometallics</jtitle><addtitle>Organometallics</addtitle><date>2007-07-30</date><risdate>2007</risdate><volume>26</volume><issue>16</issue><spage>4031</spage><epage>4037</epage><pages>4031-4037</pages><issn>0276-7333</issn><eissn>1520-6041</eissn><abstract>A number of ruthenaborane clusters have been prepared containing the {(η-C5Me5)Ru(PMe3)} fragment. Reaction of [(η-C5Me5)Ru(PMe3)H3] with 1 equiv of BH3·thf gives [(η-C5Me5)Ru(PMe3)BH4] (1), which reacts further with another equivalent of BH3·thf to give [(η-C5Me5)Ru(PMe3)B2H7] (2) in nearly quantitative yield. Thermolysis of 2 in solution at 60 °C gives a mixture of 1, arachno-2-[(η-C5Me5)Ru(PMe3)B3H8] (3), and arachno-1-[(η-C5Me5)Ru(PMe3)B3H8] (4). Thermolysis of the wing isomer 3 in solution at 100 °C gives 100% conversion to the hinge isomer 4. Thermolysis in a solution of arachno-3-[(η-C5Me5)Ru(PMe3)B4H9] also gives 4 and 1. The borohydride 1 reacts with pentaborane(9) to give four ruthenaborane clusters, compound 3, nido-2-[(η-C5Me5)RuB5H10] (5), arachno-2-[(η-C5Me5)Ru(PMe3)B5H8] (6), and arachno-3-[(η-C5Me5)Ru(PMe3)B4H9] (7). Thermolysis of 5 in solution gives nido-1-[(η-C5Me5)RuB5H10] (8) in good yield. Compound 5 deprotonates cleanly at the unique basal B−H−B bridge on reaction with KH in thf to form nido-2-[(η-C5Me5)RuB5H9 -][K+] (9). Compound 8 deprotonates cleanly at a B−H−B bridge on reaction with KH in thf to form fluxional nido-1-[(η-C5Me5)RuB5H9 -][K+] (10). The X-ray crystal structure of 3 is reported.</abstract><pub>American Chemical Society</pub><doi>10.1021/om700323g</doi><tpages>7</tpages></addata></record>
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