Ethanol Upgrading with N,N,N-Pincer-Based Ru Catalysts: Delineating Key Factors Governing Catalyst Evolution and Stability

The 5-CH3-bpi (bpi = 1,3-bis(2′-pyridylimino)isoindolate) ruthenium catalyst is among the most active catalysts to generate higher order alcohols from ethanol, via the Guerbet reaction, yet the reason(s) for this beneficial CH3-subsitution position (5- relative to 4- and 6-) were not known. To und...

Full description

Saved in:

Bibliographic Details
Published in:	ACS catalysis Vol. 14; no. 11; pp. 8456 - 8462
Main Authors:	Farris, Benjamin M., Davies, Alex M., Stephenson, Corey R. J., Szymczak, Nathaniel K.
Format:	Journal Article
Language:	English
Published:	United States American Chemical Society 15-05-2024 American Chemical Society (ACS)
Subjects:	(de)hydrogenation 09 BIOMASS FUELS alcohols catalysts chemical reactions decarbonylation ethanol Guerbet ligands ruthenium Guerbet ruthenium (de)hydrogenation decarbonylation ethanol
Online Access:	Get full text
Tags:	Add Tag No Tags, Be the first to tag this record!

Abstract	The 5-CH3-bpi (bpi = 1,3-bis(2′-pyridylimino)isoindolate) ruthenium catalyst is among the most active catalysts to generate higher order alcohols from ethanol, via the Guerbet reaction, yet the reason(s) for this beneficial CH3-subsitution position (5- relative to 4- and 6-) were not known. To understand the influence of this unique positional activity, we report a mechanistic investigation of the N,N,N-pincer Ru(bpi)(PPh3)2Cl catalyst. In situ IR and ex situ NMR/ESI-MS analyses of catalytic reactions identified a series of Ru carbonyl species generated during catalysis. We find that the primary decomposition pathway is via hydrogenolysis of the bpi ligands and that incorporating a methyl group at the 5-position disfavors this deactivation pathway.
AbstractList	The 5-CH3-bpi (bpi = 1,3-bis(2'-pyridylimino)isoindolate) ruthenium catalyst is among the most active catalysts to generate higher order alcohols from ethanol, via the Guerbet reaction, yet the reason(s) for this beneficial CH3-subsitution position (5- relative to 4- and 6-) were not known. To understand the influence of this unique positional activity, we report a mechanistic investigation of the N,N,N-pincer Ru(bpi)(PPh3)2Cl catalyst. In situ IR and ex situ NMR/ESI-MS analyses of catalytic reactions identified a series of Ru carbonyl species generated during catalysis. Here, we find that the primary decomposition pathway is via hydrogenolysis of the bpi ligands and that incorporating a methyl group at the 5-position disfavors this deactivation pathway. The 5-CH3-bpi (bpi = 1,3-bis(2′-pyridylimino)isoindolate) ruthenium catalyst is among the most active catalysts to generate higher order alcohols from ethanol, via the Guerbet reaction, yet the reason(s) for this beneficial CH3-subsitution position (5- relative to 4- and 6-) were not known. To understand the influence of this unique positional activity, we report a mechanistic investigation of the N,N,N-pincer Ru(bpi)(PPh3)2Cl catalyst. In situ IR and ex situ NMR/ESI-MS analyses of catalytic reactions identified a series of Ru carbonyl species generated during catalysis. We find that the primary decomposition pathway is via hydrogenolysis of the bpi ligands and that incorporating a methyl group at the 5-position disfavors this deactivation pathway.
Author	Stephenson, Corey R. J. Davies, Alex M. Farris, Benjamin M. Szymczak, Nathaniel K.
Author_xml	– sequence: 1 givenname: Benjamin M. surname: Farris fullname: Farris, Benjamin M. – sequence: 2 givenname: Alex M. surname: Davies fullname: Davies, Alex M. – sequence: 3 givenname: Corey R. J. orcidid: 0000-0002-2443-5514 surname: Stephenson fullname: Stephenson, Corey R. J. email: crjsteph@umich.edu – sequence: 4 givenname: Nathaniel K. orcidid: 0000-0002-1296-1445 surname: Szymczak fullname: Szymczak, Nathaniel K. email: nszym@umich.edu
BackLink	https://www.osti.gov/biblio/2371721$$D View this record in Osti.gov
BookMark	eNp1kE1PAjEQhhujiYjcPTaeWezHdnfxpghoJGoUz01pu1CytqQtmPXXuxsg8WLn0MnM885k3gtwap3VAFxhNMCI4BshgxRRVINUIkwzfAI6BDOWsJSy0z_5OeiFsEbNS1lW5KgDfsZxJayr4Odm6YUydgm_TVzBl34TyZuxUvvkXgSt4PsWjtoldYjhFj7oylgtYqt41jWcCBmdD3DqdtrbtnqE4Xjnqm00zkJhFfyIYmEqE-tLcFaKKuje4e-C-WQ8Hz0ms9fp0-hulgiSoZgoiXKi2LDIyoIsCNGSqlSKjKaLTOoCiVKlFCORFyorsR4qRugQY0X0oqAZo11wvR_rQjQ8SBO1XElnrZaRE5rjnOAGQntIeheC1yXfePMlfM0x4q3F_GgxP1jcSPp7SdPha7f1tjnif_wX3TiCFA
Cites_doi	10.1021/jacs.6b05433 10.1002/ange.201809333 10.1021/acs.organomet.1c00217 10.1002/anie.201303723 10.1039/C8CC04370A 10.1039/jr9640003466 10.1016/j.ymben.2007.08.003 10.1021/acscatal.5b01327 10.1021/jacs.7b05939 10.1002/ejoc.201900541 10.1021/om9910064 10.1002/(SICI)1521-3773(19990401)38:7<870:AID-ANIE870>3.0.CO;2-3 10.1039/C4EM00150H 10.1021/om049716j 10.1016/j.enconman.2010.08.013 10.1021/acscatal.7b03653 10.1021/ja01064a009 10.1021/om960817u 10.1021/acs.joc.2c02356 10.1016/j.scitotenv.2013.04.093 10.1021/acscatal.5b00952 10.1016/j.jcat.2021.11.027 10.1021/acscatal.2c01570 10.1021/ic00296a043 10.1246/cl.2009.838 10.1002/ejoc.201101616 10.1021/om00031a024 10.1039/C5CC09913G 10.1016/j.chempr.2020.11.013 10.1039/C7CY01553D 10.1021/cs4011343 10.1039/C4GC00510D 10.1039/D1CY00322D 10.1039/D1EE02540F 10.1021/acscatal.6b01883 10.1002/14356007.a09_587.pub2 10.1021/jacs.5b10257
ContentType	Journal Article
Copyright	2024 American Chemical Society
Copyright_xml	– notice: 2024 American Chemical Society
CorporateAuthor	Univ. of Michigan, Ann Arbor, MI (United States)
CorporateAuthor_xml	– name: Univ. of Michigan, Ann Arbor, MI (United States)
DBID	AAYXX CITATION OTOTI
DOI	10.1021/acscatal.4c01361
DatabaseName	CrossRef OSTI.GOV
DatabaseTitle	CrossRef
DatabaseTitleList
DeliveryMethod	fulltext_linktorsrc
Discipline	Chemistry
EISSN	2155-5435
EndPage	8462
ExternalDocumentID	2371721 10_1021_acscatal_4c01361 c709666622
GroupedDBID	.K2 55A 7~N AABXI AAHBH ABFRP ABJNI ABMVS ABQRX ABUCX ACGFO ACGFS ACS ADHLV AEESW AENEX AFEFF AHGAQ ALMA_UNASSIGNED_HOLDINGS AQSVZ BAANH CUPRZ EBS ED~ GGK GNL IH9 JG~ RNS ROL UI2 VF5 VG9 W1F AAYXX CITATION OTOTI
ID	FETCH-LOGICAL-a260t-dc072d5986f82b22ec3d4ca634b6ce80afd4310a78d6f1e9d523911d2eb83653
IEDL.DBID	ACS
ISSN	2155-5435
IngestDate	Tue Jun 25 16:20:54 EDT 2024 Fri Aug 23 01:36:53 EDT 2024 Tue Jun 25 16:50:45 EDT 2024
IsPeerReviewed	true
IsScholarly	true
Issue	11
Keywords	Guerbet ruthenium (de)hydrogenation decarbonylation ethanol
Language	English
LinkModel	DirectLink
MergedId	FETCHMERGED-LOGICAL-a260t-dc072d5986f82b22ec3d4ca634b6ce80afd4310a78d6f1e9d523911d2eb83653
Notes	USDOE Office of Science (SC), Basic Energy Sciences (BES) SC0020191
ORCID	0000-0002-1296-1445 0000-0002-2443-5514 0000000224435514 0000000212961445
PageCount	7
ParticipantIDs	osti_scitechconnect_2371721 crossref_primary_10_1021_acscatal_4c01361 acs_journals_10_1021_acscatal_4c01361
PublicationCentury	2000
PublicationDate	2024-05-15
PublicationDateYYYYMMDD	2024-05-15
PublicationDate_xml	– month: 05 year: 2024 text: 2024-05-15 day: 15
PublicationDecade	2020
PublicationPlace	United States
PublicationPlace_xml	– name: United States
PublicationTitle	ACS catalysis
PublicationTitleAlternate	ACS Catal
PublicationYear	2024
Publisher	American Chemical Society American Chemical Society (ACS)
Publisher_xml	– name: American Chemical Society – name: American Chemical Society (ACS)
References	ref9/cit9 ref6/cit6 ref36/cit36 ref3/cit3 ref27/cit27 ref18/cit18 Guerbet M. (ref11/cit11) 1909; 149 ref25/cit25 ref16/cit16 ref29/cit29 ref32/cit32 ref23/cit23 ref39/cit39 ref14/cit14 ref8/cit8 ref5/cit5 ref31/cit31 ref2/cit2 ref34/cit34 ref37/cit37 ref28/cit28 ref40/cit40 ref20/cit20 ref17/cit17 ref26/cit26 ref35/cit35 ref19/cit19 ref21/cit21 ref12/cit12 ref15/cit15 ref42/cit42 ref41/cit41 ref22/cit22 ref13/cit13 Guerbet M. (ref10/cit10) 1899; 128 ref33/cit33 ref4/cit4 ref30/cit30 ref1/cit1 ref24/cit24 ref38/cit38 ref7/cit7
References_xml	– ident: ref21/cit21 doi: 10.1021/jacs.6b05433 – ident: ref31/cit31 – ident: ref12/cit12 doi: 10.1002/ange.201809333 – ident: ref20/cit20 doi: 10.1021/acs.organomet.1c00217 – ident: ref15/cit15 doi: 10.1002/anie.201303723 – ident: ref29/cit29 doi: 10.1039/C8CC04370A – ident: ref35/cit35 doi: 10.1039/jr9640003466 – ident: ref5/cit5 doi: 10.1016/j.ymben.2007.08.003 – ident: ref16/cit16 doi: 10.1021/acscatal.5b01327 – ident: ref22/cit22 doi: 10.1021/jacs.7b05939 – ident: ref32/cit32 doi: 10.1002/ejoc.201900541 – ident: ref37/cit37 doi: 10.1021/om9910064 – ident: ref40/cit40 doi: 10.1002/(SICI)1521-3773(19990401)38:7<870:AID-ANIE870>3.0.CO;2-3 – volume: 149 start-page: 129 year: 1909 ident: ref11/cit11 publication-title: C. R. Acad. Sci. Paris contributor: fullname: Guerbet M. – ident: ref1/cit1 doi: 10.1039/C4EM00150H – ident: ref36/cit36 doi: 10.1021/om049716j – ident: ref3/cit3 doi: 10.1016/j.enconman.2010.08.013 – ident: ref19/cit19 doi: 10.1021/acscatal.7b03653 – ident: ref34/cit34 doi: 10.1021/ja01064a009 – ident: ref38/cit38 doi: 10.1021/om960817u – ident: ref7/cit7 doi: 10.1021/acs.joc.2c02356 – ident: ref2/cit2 doi: 10.1016/j.scitotenv.2013.04.093 – ident: ref28/cit28 doi: 10.1021/acscatal.5b00952 – ident: ref26/cit26 doi: 10.1016/j.jcat.2021.11.027 – ident: ref25/cit25 doi: 10.1021/acscatal.2c01570 – ident: ref30/cit30 doi: 10.1021/ic00296a043 – ident: ref13/cit13 doi: 10.1246/cl.2009.838 – ident: ref41/cit41 doi: 10.1002/ejoc.201101616 – ident: ref39/cit39 doi: 10.1021/om00031a024 – ident: ref24/cit24 doi: 10.1039/C5CC09913G – ident: ref27/cit27 – volume: 128 start-page: 1002 year: 1899 ident: ref10/cit10 publication-title: C. R. Acad. Sci. Paris contributor: fullname: Guerbet M. – ident: ref23/cit23 doi: 10.1016/j.chempr.2020.11.013 – ident: ref17/cit17 doi: 10.1039/C7CY01553D – ident: ref4/cit4 doi: 10.1021/cs4011343 – ident: ref14/cit14 doi: 10.1039/C4GC00510D – ident: ref42/cit42 – ident: ref33/cit33 doi: 10.1039/D1CY00322D – ident: ref9/cit9 doi: 10.1039/D1EE02540F – ident: ref6/cit6 doi: 10.1021/acscatal.6b01883 – ident: ref8/cit8 doi: 10.1002/14356007.a09_587.pub2 – ident: ref18/cit18 doi: 10.1021/jacs.5b10257
SSID	ssj0000456870
Score	2.4591482
Snippet	The 5-CH3-bpi (bpi = 1,3-bis(2′-pyridylimino)isoindolate) ruthenium catalyst is among the most active catalysts to generate higher order alcohols from... The 5-CH3-bpi (bpi = 1,3-bis(2'-pyridylimino)isoindolate) ruthenium catalyst is among the most active catalysts to generate higher order alcohols from ethanol,...
SourceID	osti crossref acs
SourceType	Open Access Repository Aggregation Database Publisher
StartPage	8456
SubjectTerms	(de)hydrogenation 09 BIOMASS FUELS alcohols catalysts chemical reactions decarbonylation ethanol Guerbet ligands ruthenium
Title	Ethanol Upgrading with N,N,N-Pincer-Based Ru Catalysts: Delineating Key Factors Governing Catalyst Evolution and Stability
URI	http://dx.doi.org/10.1021/acscatal.4c01361 https://www.osti.gov/biblio/2371721
Volume	14
hasFullText	1
inHoldings	1
isFullTextHit
isPrint
link	http://sdu.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwlV1LS8NAEF60HvTiW6xV2YMeBFeTzeZRbxpTCkIRW8Fb2OxuRJC0NKlQf70zeUgVESW3sJmEmZ3MN4-dIeTEBZupFLcZgH2XCcDILDFOyowlQLOUA24RHhTuD_3BU3AbLbbJ-Z7B5_alVHkZybgQCvuLgaezwn0ACgiDwuFnPAWhSVDOhgMj5jIXYECdlfyJCNoilX-xRa0x6NSCbelt_OerNsl6jSDpdSXyLbJksm2yGjaD23bIe4Th8PErfZw8T8sSeYrRVjo4h4vdv4CYp-wGrJemDzMaIv15XuRX9BbPpiOGhCfuzJz2qlk8tJrHi3ebxTR6q7cslZmmgFjLGtv5Lhn1olHYZ_WIBSbBkSmYVpbPNfZoTwOecG6Uo4WSniMST5nAkqkGhGFJP9BeapuuBr8Vfo-amyRwPNfZI61snJl9QrnQBviAY8UT4etukgANKbURAUI6r01OgWdxrSF5XCa_uR03jIxrRrbJWSOTeFI13PhlbQeFFgNYwI63CkuDVBFzx0fH9uCPb-yQNQ5IBUsCbPeQtIrpzByR5VzPjsst9gEk7cv0
link.rule.ids	230,315,782,786,887,2769,27085,27933,27934,56747,56797
linkProvider	American Chemical Society
linkToHtml	http://sdu.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwnV1LT8MwDI5gHMaFN2KMRw5wQCLQpulj3KBsGtqYEBsSt6pNUoSEumntkMavx-6Dh4QQQr1FqRvZTv3ZcWxCjmywmVJykwHYt5kAjMwibcVMGwJ2lrTALcKLwt2hO3j0rttYJses7sLAIlKglOaH-J_VBcxzGMsDGmdCYpkxcHiWbAewMKIhf_gRVkGE4uUt4sCW2cwGNFAeTv5EBE2STL-ZpNoYttYXE9NZ_cfi1shKiSfpZaEA62RBJxuk7ldt3DbJWxuD4-MX-jB5muYJ8xRjr3RwCg-7ewahT9kV2DJF72fUR_rzNEsv6DXeVEdECW_09Jx2is48tOjOi6PVZNp-LRWYhomigF_zjNv5Fhl12iO_y8qGCywEtyZjShouV1ixPfZ4xLmWlhIydCwROVJ7RhgrwBtG6HrKiU3dUuDFws9ScR15lmNb26SWjBO9QygXSgMfsMl4JFzViiKgEYZKCw8BntMgx8CzoNwvaZAfhXMzqBgZlIxskJNKNMGkKL_xy9wmyi4A6ID1byUmCsks4JaLbu7uH794SOrd0W0_6N8Mek2yzAHDYLKAae-RWjad6X2ymKrZQa5175I41GE
linkToPdf	http://sdu.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwnV1LS8NAEF60gnrxLdb62IMeBFeTzbPeappQqZRiK3gLye5GBElLkwr11zuThyiIiOS2bCbL7E7mm8fOEHJmgc4UgusMwL7FTMDILFZGwpRmgmQJA8wivCjcGzmDJ7frY5kcq74LA4vIgFJWBPFRqqcyqSoM6NcwXjg1rkyBpcbA6FmxbKeNNlfHG326VhCluEWbONBnFrMAEVQByp-IoFoS2Te11JiAeH1RM8HmPxe4RTYqXEk75UHYJksq3SFrXt3ObZe8--gkn7zSx-nzrEicp-iDpYNLeNjwBTZ_xm5Bp0n6MKce0l9keXZDu3hjHZElvNFXCxqUHXpo2aUXR-vJ1H-rDjKNUkkBxxaZt4s9Mg78sddjVeMFFoF5kzMpNIdLrNyeuDzmXAlDmiKyDTO2hXK1KJGAO7TIcaWd6KotwZqFn6bkKnYN2zL2SSOdpOqAUG5KBXzAZuOx6ch2HAONKJLKdBHo2U1yDjwLK7nJwiIkzvWwZmRYMbJJLurtCadlGY5f5rZw_0KAEFgHV2DCkMhDbjho7h7-8YunZHXYDcL7u0G_RdY5QBnMGdCtI9LIZ3N1TJYzOT8pDt4HmqDW5A
openUrl	ctx_ver=Z39.88-2004&ctx_enc=info%3Aofi%2Fenc%3AUTF-8&rfr_id=info%3Asid%2Fsummon.serialssolutions.com&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal&rft.genre=article&rft.atitle=Ethanol+Upgrading+with+N%2CN%2CN-Pincer-Based+Ru+Catalysts%3A+Delineating+Key+Factors+Governing+Catalyst+Evolution+and+Stability&rft.jtitle=ACS+catalysis&rft.au=Farris%2C+Benjamin+M.&rft.au=Davies%2C+Alex+M.&rft.au=Stephenson%2C+Corey+R.+J.&rft.au=Szymczak%2C+Nathaniel+K.&rft.date=2024-05-15&rft.pub=American+Chemical+Society+%28ACS%29&rft.issn=2155-5435&rft.eissn=2155-5435&rft.volume=14&rft.issue=11&rft_id=info:doi/10.1021%2Facscatal.4c01361&rft.externalDocID=2371721
thumbnail_l	http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/lc.gif&issn=2155-5435&client=summon
thumbnail_m	http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/mc.gif&issn=2155-5435&client=summon
thumbnail_s	http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/sc.gif&issn=2155-5435&client=summon