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E−H Bond Activation Reactions (E = H, C, Si, Ge) at Ruthenium: Terminal Phosphides, Silylenes, and Germylenes
The placement of a strongly trans-influencing ligand on a ruthenium center opposite an anchoring silyl group of the tetradentate tripodal tris(phosphino)silyl ligand, [SiPPh 3]− ([SiPPh 3]− = tris(2-(diphenylphosphino)phenyl)silyl), has been explored. Installation of alkyl or terminal phosphide liga...
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Published in: | Organometallics 2009-07, Vol.28 (13), p.3744-3753 |
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creator | Takaoka, Ayumi Mendiratta, Arjun Peters, Jonas C |
description | The placement of a strongly trans-influencing ligand on a ruthenium center opposite an anchoring silyl group of the tetradentate tripodal tris(phosphino)silyl ligand, [SiPPh 3]− ([SiPPh 3]− = tris(2-(diphenylphosphino)phenyl)silyl), has been explored. Installation of alkyl or terminal phosphide ligands trans to the anchoring silyl group affords the complexes [SiPPh 3]RuR (R = Me (2), CH2Ph (4), PPh2 (5), P i Pr2 (6)). Complexes 2, 4, and 5 are thermally unstable. Complexes 2 and 4 decay to the cyclometalated complex [SiPPh 2P′Ph]Ru (3), whereas complex 5 decays to the cyclometalated phosphine adduct [SiPPh 2P′Ph]Ru(PHPh2) (7). Complex 3 is found to effect E−H (E = H, C, Si, Ge) bond activation of substrates such as secondary silanes and germanes to yield the structurally unusual silylene complexes [SiPPh 3]Ru(H)(SiRR′) (R = R′ = Ph (10a), R = Ph R′ = Me (10b)) and the germylene complex [SiPPh 3]Ru(H)(GeR2) (R = Ph) (11) via double E−H activation transformations. Both theory and experiments suggest electrophilic character at the silylene moiety. Reaction of 3 with catecholborane, in contrast to silanes and germanes, results in insertion of the B−H unit into the M−C bond of the cyclometalated species to yield the borate complex [SiPPh 2PPh-B(cat)]Ru(μ-H) (14). Complex 3 also reacts with bis(catecholato)diboron to yield a similar complex, [SiPPh 2PC6H3B(cat)-B(cat)]Ru(μ-H) (15), with selective borylation of an ortho C−H bond. |
doi_str_mv | 10.1021/om900216u |
format | article |
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Installation of alkyl or terminal phosphide ligands trans to the anchoring silyl group affords the complexes [SiPPh 3]RuR (R = Me (2), CH2Ph (4), PPh2 (5), P i Pr2 (6)). Complexes 2, 4, and 5 are thermally unstable. Complexes 2 and 4 decay to the cyclometalated complex [SiPPh 2P′Ph]Ru (3), whereas complex 5 decays to the cyclometalated phosphine adduct [SiPPh 2P′Ph]Ru(PHPh2) (7). Complex 3 is found to effect E−H (E = H, C, Si, Ge) bond activation of substrates such as secondary silanes and germanes to yield the structurally unusual silylene complexes [SiPPh 3]Ru(H)(SiRR′) (R = R′ = Ph (10a), R = Ph R′ = Me (10b)) and the germylene complex [SiPPh 3]Ru(H)(GeR2) (R = Ph) (11) via double E−H activation transformations. Both theory and experiments suggest electrophilic character at the silylene moiety. Reaction of 3 with catecholborane, in contrast to silanes and germanes, results in insertion of the B−H unit into the M−C bond of the cyclometalated species to yield the borate complex [SiPPh 2PPh-B(cat)]Ru(μ-H) (14). Complex 3 also reacts with bis(catecholato)diboron to yield a similar complex, [SiPPh 2PC6H3B(cat)-B(cat)]Ru(μ-H) (15), with selective borylation of an ortho C−H bond.</description><identifier>ISSN: 0276-7333</identifier><identifier>EISSN: 1520-6041</identifier><identifier>DOI: 10.1021/om900216u</identifier><language>eng</language><publisher>American Chemical Society</publisher><ispartof>Organometallics, 2009-07, Vol.28 (13), p.3744-3753</ispartof><rights>Copyright © 2009 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a325t-b582ec3814c66ef98bbf36598080235cba3f8242d4778b9b870246e8b04c71ee3</citedby><cites>FETCH-LOGICAL-a325t-b582ec3814c66ef98bbf36598080235cba3f8242d4778b9b870246e8b04c71ee3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Takaoka, Ayumi</creatorcontrib><creatorcontrib>Mendiratta, Arjun</creatorcontrib><creatorcontrib>Peters, Jonas C</creatorcontrib><title>E−H Bond Activation Reactions (E = H, C, Si, Ge) at Ruthenium: Terminal Phosphides, Silylenes, and Germylenes</title><title>Organometallics</title><addtitle>Organometallics</addtitle><description>The placement of a strongly trans-influencing ligand on a ruthenium center opposite an anchoring silyl group of the tetradentate tripodal tris(phosphino)silyl ligand, [SiPPh 3]− ([SiPPh 3]− = tris(2-(diphenylphosphino)phenyl)silyl), has been explored. Installation of alkyl or terminal phosphide ligands trans to the anchoring silyl group affords the complexes [SiPPh 3]RuR (R = Me (2), CH2Ph (4), PPh2 (5), P i Pr2 (6)). Complexes 2, 4, and 5 are thermally unstable. Complexes 2 and 4 decay to the cyclometalated complex [SiPPh 2P′Ph]Ru (3), whereas complex 5 decays to the cyclometalated phosphine adduct [SiPPh 2P′Ph]Ru(PHPh2) (7). Complex 3 is found to effect E−H (E = H, C, Si, Ge) bond activation of substrates such as secondary silanes and germanes to yield the structurally unusual silylene complexes [SiPPh 3]Ru(H)(SiRR′) (R = R′ = Ph (10a), R = Ph R′ = Me (10b)) and the germylene complex [SiPPh 3]Ru(H)(GeR2) (R = Ph) (11) via double E−H activation transformations. Both theory and experiments suggest electrophilic character at the silylene moiety. Reaction of 3 with catecholborane, in contrast to silanes and germanes, results in insertion of the B−H unit into the M−C bond of the cyclometalated species to yield the borate complex [SiPPh 2PPh-B(cat)]Ru(μ-H) (14). Complex 3 also reacts with bis(catecholato)diboron to yield a similar complex, [SiPPh 2PC6H3B(cat)-B(cat)]Ru(μ-H) (15), with selective borylation of an ortho C−H bond.</description><issn>0276-7333</issn><issn>1520-6041</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2009</creationdate><recordtype>article</recordtype><recordid>eNptkEFLwzAcxYMoOKcHv0EugsKq_yRtkgoe5pibMFDmPJckS1lG24ymFfYNPPsR_SS2TDx5eu_BjwfvIXRJ4JYAJXe-TKFT3h6hAUkoRBxicowGQAWPBGPsFJ2FsAUALhgdID_9_vya40dfrfHYNO5DNc5XeGmV6U3A11P8gOcjPBnhNzfCM3uDVYOXbbOxlWvLe7yydekqVeDXjQ-7jVvb0KPFvrBVb1XXPOuYQz5HJ7kqgr341SF6f5quJvNo8TJ7nowXkWI0aSKdSGoNkyQ2nNs8lVrnjCepBAmUJUYrlksa03UshNSplgJozK3UEBtBrGVDdHPoNbUPobZ5tqtdqep9RiDrn8r-nurYqwOrTMi2vq27NeEf7gdwQWYL</recordid><startdate>20090713</startdate><enddate>20090713</enddate><creator>Takaoka, Ayumi</creator><creator>Mendiratta, Arjun</creator><creator>Peters, Jonas C</creator><general>American Chemical Society</general><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20090713</creationdate><title>E−H Bond Activation Reactions (E = H, C, Si, Ge) at Ruthenium: Terminal Phosphides, Silylenes, and Germylenes</title><author>Takaoka, Ayumi ; Mendiratta, Arjun ; Peters, Jonas C</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a325t-b582ec3814c66ef98bbf36598080235cba3f8242d4778b9b870246e8b04c71ee3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2009</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Takaoka, Ayumi</creatorcontrib><creatorcontrib>Mendiratta, Arjun</creatorcontrib><creatorcontrib>Peters, Jonas C</creatorcontrib><collection>CrossRef</collection><jtitle>Organometallics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Takaoka, Ayumi</au><au>Mendiratta, Arjun</au><au>Peters, Jonas C</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>E−H Bond Activation Reactions (E = H, C, Si, Ge) at Ruthenium: Terminal Phosphides, Silylenes, and Germylenes</atitle><jtitle>Organometallics</jtitle><addtitle>Organometallics</addtitle><date>2009-07-13</date><risdate>2009</risdate><volume>28</volume><issue>13</issue><spage>3744</spage><epage>3753</epage><pages>3744-3753</pages><issn>0276-7333</issn><eissn>1520-6041</eissn><abstract>The placement of a strongly trans-influencing ligand on a ruthenium center opposite an anchoring silyl group of the tetradentate tripodal tris(phosphino)silyl ligand, [SiPPh 3]− ([SiPPh 3]− = tris(2-(diphenylphosphino)phenyl)silyl), has been explored. Installation of alkyl or terminal phosphide ligands trans to the anchoring silyl group affords the complexes [SiPPh 3]RuR (R = Me (2), CH2Ph (4), PPh2 (5), P i Pr2 (6)). Complexes 2, 4, and 5 are thermally unstable. Complexes 2 and 4 decay to the cyclometalated complex [SiPPh 2P′Ph]Ru (3), whereas complex 5 decays to the cyclometalated phosphine adduct [SiPPh 2P′Ph]Ru(PHPh2) (7). Complex 3 is found to effect E−H (E = H, C, Si, Ge) bond activation of substrates such as secondary silanes and germanes to yield the structurally unusual silylene complexes [SiPPh 3]Ru(H)(SiRR′) (R = R′ = Ph (10a), R = Ph R′ = Me (10b)) and the germylene complex [SiPPh 3]Ru(H)(GeR2) (R = Ph) (11) via double E−H activation transformations. Both theory and experiments suggest electrophilic character at the silylene moiety. Reaction of 3 with catecholborane, in contrast to silanes and germanes, results in insertion of the B−H unit into the M−C bond of the cyclometalated species to yield the borate complex [SiPPh 2PPh-B(cat)]Ru(μ-H) (14). Complex 3 also reacts with bis(catecholato)diboron to yield a similar complex, [SiPPh 2PC6H3B(cat)-B(cat)]Ru(μ-H) (15), with selective borylation of an ortho C−H bond.</abstract><pub>American Chemical Society</pub><doi>10.1021/om900216u</doi><tpages>10</tpages></addata></record> |
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title | E−H Bond Activation Reactions (E = H, C, Si, Ge) at Ruthenium: Terminal Phosphides, Silylenes, and Germylenes |
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