Dihydrogen Complexes of Iridium and Rhodium

Dihydrogen Complexes of Iridium and Rhodium

A series of iridium and rhodium pincer complexes have been synthesized and characterized: [(POCOP)­Ir­(H)­(H2)] [BArf 4] (1-H 3 ), (POCOP)­Rh­(H2) (2-H 2 ), [(PONOP)­Ir­(C2H4)] [BArf 4] (3-C 2 H 4 ), [(PONOP)­Ir­(H)2)] [BArf 4] (3-H 2 ), [(PONOP)­Rh­(C2H4)] [BArf 4] (4-C 2 H 4 ) and [(PONOP)­Rh­(H2)...

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Veröffentlicht in:Inorganic chemistry 2012-04, Vol.51 (8), p.4672-4678
Hauptverfasser: Findlater, Michael, Schultz, Katherine M, Bernskoetter, Wesley H, Cartwright-Sykes, Alison, Heinekey, D. Michael, Brookhart, Maurice
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container_end_page 4678
container_issue 8
container_start_page 4672
container_title Inorganic chemistry
container_volume 51
creator Findlater, Michael
Schultz, Katherine M
Bernskoetter, Wesley H
Cartwright-Sykes, Alison
Heinekey, D. Michael
Brookhart, Maurice
description A series of iridium and rhodium pincer complexes have been synthesized and characterized: [(POCOP)­Ir­(H)­(H2)] [BArf 4] (1-H 3 ), (POCOP)­Rh­(H2) (2-H 2 ), [(PONOP)­Ir­(C2H4)] [BArf 4] (3-C 2 H 4 ), [(PONOP)­Ir­(H)2)] [BArf 4] (3-H 2 ), [(PONOP)­Rh­(C2H4)] [BArf 4] (4-C 2 H 4 ) and [(PONOP)­Rh­(H2)] [BArf 4] (4-H 2 ) (POCOP = κ3-C6H3-2,6-[OP­(tBu)2]2; PONOP = 2,6-(tBu2PO)2C5H3N; BArf 4 = tetrakis­(3,5-trifluoromethylphenyl)­borate). The nature of the dihydrogen–metal interaction was probed using NMR spectroscopic studies. Complexes 1-H 3 , 2-H 2 , and 4-H 2 retain the H–H bond and are classified as η2-dihydrogen adducts. In contrast, complex 3-H 2 is best described as a classical dihydride system. The presence of bound dihydrogen was determined using both T1 and 1 J HD coupling values: T 1 = 14 ms, 1 J HD = 33 Hz for the dihydrogen ligand in 1-H 3 , T 1(min) = 23 ms, 1 J HD = 32 Hz for 2-H 2 , T 1(min) = 873 ms for 3-H 2 , T 1(min) = 33 ms, 1 J HD = 30.1 Hz for 4-H 2 .
doi_str_mv 10.1021/ic202630x
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Michael ; Brookhart, Maurice</creator><creatorcontrib>Findlater, Michael ; Schultz, Katherine M ; Bernskoetter, Wesley H ; Cartwright-Sykes, Alison ; Heinekey, D. Michael ; Brookhart, Maurice</creatorcontrib><description>A series of iridium and rhodium pincer complexes have been synthesized and characterized: [(POCOP)­Ir­(H)­(H2)] [BArf 4] (1-H 3 ), (POCOP)­Rh­(H2) (2-H 2 ), [(PONOP)­Ir­(C2H4)] [BArf 4] (3-C 2 H 4 ), [(PONOP)­Ir­(H)2)] [BArf 4] (3-H 2 ), [(PONOP)­Rh­(C2H4)] [BArf 4] (4-C 2 H 4 ) and [(PONOP)­Rh­(H2)] [BArf 4] (4-H 2 ) (POCOP = κ3-C6H3-2,6-[OP­(tBu)2]2; PONOP = 2,6-(tBu2PO)2C5H3N; BArf 4 = tetrakis­(3,5-trifluoromethylphenyl)­borate). The nature of the dihydrogen–metal interaction was probed using NMR spectroscopic studies. Complexes 1-H 3 , 2-H 2 , and 4-H 2 retain the H–H bond and are classified as η2-dihydrogen adducts. In contrast, complex 3-H 2 is best described as a classical dihydride system. The presence of bound dihydrogen was determined using both T1 and 1 J HD coupling values: T 1 = 14 ms, 1 J HD = 33 Hz for the dihydrogen ligand in 1-H 3 , T 1(min) = 23 ms, 1 J HD = 32 Hz for 2-H 2 , T 1(min) = 873 ms for 3-H 2 , T 1(min) = 33 ms, 1 J HD = 30.1 Hz for 4-H 2 .</description><identifier>ISSN: 0020-1669</identifier><identifier>EISSN: 1520-510X</identifier><identifier>DOI: 10.1021/ic202630x</identifier><identifier>PMID: 22364621</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><ispartof>Inorganic chemistry, 2012-04, Vol.51 (8), p.4672-4678</ispartof><rights>Copyright © 2012 American Chemical Society</rights><rights>2012 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a315t-7d5af1a2ba1519450e3dd41fe5e11dcb9ed675acb2d084922c8b24d71e4519cc3</citedby><cites>FETCH-LOGICAL-a315t-7d5af1a2ba1519450e3dd41fe5e11dcb9ed675acb2d084922c8b24d71e4519cc3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ic202630x$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ic202630x$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2751,27055,27903,27904,56716,56766</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/22364621$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Findlater, Michael</creatorcontrib><creatorcontrib>Schultz, Katherine M</creatorcontrib><creatorcontrib>Bernskoetter, Wesley H</creatorcontrib><creatorcontrib>Cartwright-Sykes, Alison</creatorcontrib><creatorcontrib>Heinekey, D. Michael</creatorcontrib><creatorcontrib>Brookhart, Maurice</creatorcontrib><title>Dihydrogen Complexes of Iridium and Rhodium</title><title>Inorganic chemistry</title><addtitle>Inorg. Chem</addtitle><description>A series of iridium and rhodium pincer complexes have been synthesized and characterized: [(POCOP)­Ir­(H)­(H2)] [BArf 4] (1-H 3 ), (POCOP)­Rh­(H2) (2-H 2 ), [(PONOP)­Ir­(C2H4)] [BArf 4] (3-C 2 H 4 ), [(PONOP)­Ir­(H)2)] [BArf 4] (3-H 2 ), [(PONOP)­Rh­(C2H4)] [BArf 4] (4-C 2 H 4 ) and [(PONOP)­Rh­(H2)] [BArf 4] (4-H 2 ) (POCOP = κ3-C6H3-2,6-[OP­(tBu)2]2; PONOP = 2,6-(tBu2PO)2C5H3N; BArf 4 = tetrakis­(3,5-trifluoromethylphenyl)­borate). The nature of the dihydrogen–metal interaction was probed using NMR spectroscopic studies. Complexes 1-H 3 , 2-H 2 , and 4-H 2 retain the H–H bond and are classified as η2-dihydrogen adducts. In contrast, complex 3-H 2 is best described as a classical dihydride system. The presence of bound dihydrogen was determined using both T1 and 1 J HD coupling values: T 1 = 14 ms, 1 J HD = 33 Hz for the dihydrogen ligand in 1-H 3 , T 1(min) = 23 ms, 1 J HD = 32 Hz for 2-H 2 , T 1(min) = 873 ms for 3-H 2 , T 1(min) = 33 ms, 1 J HD = 30.1 Hz for 4-H 2 .</description><issn>0020-1669</issn><issn>1520-510X</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2012</creationdate><recordtype>article</recordtype><recordid>eNpt0EtLw0AUBeBBFFurC_-AZCMoEr13XjFLqa9CQRAFd2EyM7EpSabONND-e6e0duXqnsXHgXsIOUe4RaB4V2sKVDJYHZAhCgqpQPg6JEOAmFHKfEBOQpgDQM64PCYDSpnkkuKQ3DzWs7Xx7tt2ydi1i8aubEhclUx8beq-TVRnkveZ2-RTclSpJtiz3R2Rz-enj_FrOn17mYwfpqliKJZpZoSqUNFSocCcC7DMGI6VFRbR6DK3RmZC6ZIauOc5pfq-pNxkaHn0WrMRudr2Lrz76W1YFm0dtG0a1VnXhwIBMBcs4yzS6y3V3oXgbVUsfN0qv46o2GxT7LeJ9mJX25etNXv5N0YEl1ugdCjmrvdd_PKfol96P2lN</recordid><startdate>20120416</startdate><enddate>20120416</enddate><creator>Findlater, Michael</creator><creator>Schultz, Katherine M</creator><creator>Bernskoetter, Wesley H</creator><creator>Cartwright-Sykes, Alison</creator><creator>Heinekey, D. 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Michael ; Brookhart, Maurice</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a315t-7d5af1a2ba1519450e3dd41fe5e11dcb9ed675acb2d084922c8b24d71e4519cc3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2012</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Findlater, Michael</creatorcontrib><creatorcontrib>Schultz, Katherine M</creatorcontrib><creatorcontrib>Bernskoetter, Wesley H</creatorcontrib><creatorcontrib>Cartwright-Sykes, Alison</creatorcontrib><creatorcontrib>Heinekey, D. Michael</creatorcontrib><creatorcontrib>Brookhart, Maurice</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Findlater, Michael</au><au>Schultz, Katherine M</au><au>Bernskoetter, Wesley H</au><au>Cartwright-Sykes, Alison</au><au>Heinekey, D. Michael</au><au>Brookhart, Maurice</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Dihydrogen Complexes of Iridium and Rhodium</atitle><jtitle>Inorganic chemistry</jtitle><addtitle>Inorg. Chem</addtitle><date>2012-04-16</date><risdate>2012</risdate><volume>51</volume><issue>8</issue><spage>4672</spage><epage>4678</epage><pages>4672-4678</pages><issn>0020-1669</issn><eissn>1520-510X</eissn><abstract>A series of iridium and rhodium pincer complexes have been synthesized and characterized: [(POCOP)­Ir­(H)­(H2)] [BArf 4] (1-H 3 ), (POCOP)­Rh­(H2) (2-H 2 ), [(PONOP)­Ir­(C2H4)] [BArf 4] (3-C 2 H 4 ), [(PONOP)­Ir­(H)2)] [BArf 4] (3-H 2 ), [(PONOP)­Rh­(C2H4)] [BArf 4] (4-C 2 H 4 ) and [(PONOP)­Rh­(H2)] [BArf 4] (4-H 2 ) (POCOP = κ3-C6H3-2,6-[OP­(tBu)2]2; PONOP = 2,6-(tBu2PO)2C5H3N; BArf 4 = tetrakis­(3,5-trifluoromethylphenyl)­borate). The nature of the dihydrogen–metal interaction was probed using NMR spectroscopic studies. Complexes 1-H 3 , 2-H 2 , and 4-H 2 retain the H–H bond and are classified as η2-dihydrogen adducts. In contrast, complex 3-H 2 is best described as a classical dihydride system. The presence of bound dihydrogen was determined using both T1 and 1 J HD coupling values: T 1 = 14 ms, 1 J HD = 33 Hz for the dihydrogen ligand in 1-H 3 , T 1(min) = 23 ms, 1 J HD = 32 Hz for 2-H 2 , T 1(min) = 873 ms for 3-H 2 , T 1(min) = 33 ms, 1 J HD = 30.1 Hz for 4-H 2 .</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>22364621</pmid><doi>10.1021/ic202630x</doi><tpages>7</tpages></addata></record>
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