Trapping of a Late-Metal Terminal Sulfido Intermediate with Phenyl Isothiocyanate

Nickel–sulfur bonds play key roles in catalysis and biological systems. In most metal complexes, sulfur acts as a bridge joining metal centers, rather than as a terminal sulfide ligand. The addition of phenyl isothiocyanate to Ni(dcpe)(Ph)(SH) afforded the dithiocarbamate complex Ni(dcpe)(κ2-S2...

Ausführliche Beschreibung

Gespeichert in:

Bibliographische Detailangaben
Veröffentlicht in:	Organometallics 2022-11, Vol.41 (22), p.3448-3453
Hauptverfasser:	Shanahan, James P., Vicic, David A., Brennessel, William W., Jones, William D.
Format:	Artikel
Sprache:	eng
Schlagworte:	Chemical reactions Kinetics Ligands Organic reactions Phenyls
Online-Zugang:	Volltext
Tags:	Tag hinzufügen Keine Tags, Fügen Sie den ersten Tag hinzu!

container_end_page	3453
container_issue	22
container_start_page	3448
container_title	Organometallics
container_volume	41
creator	Shanahan, James P. Vicic, David A. Brennessel, William W. Jones, William D.
description	Nickel–sulfur bonds play key roles in catalysis and biological systems. In most metal complexes, sulfur acts as a bridge joining metal centers, rather than as a terminal sulfide ligand. The addition of phenyl isothiocyanate to Ni(dcpe)(Ph)(SH) afforded the dithiocarbamate complex Ni(dcpe)(κ2-S2CNPh) with the loss of benzene. The reaction was monitored by UV–visible spectroscopy under pseudo-first-order rate conditions and showed limited dependence on isothiocyanate concentration, suggesting that the reaction proceeds through an intermediate terminal sulfido nickel complex. The values of ΔH ⧧ and ΔS ⧧ for the reaction were found to be 18.6 ± 1.5 kcal/mol and −17.8 ± 4.7 eu, respectively. Full characterization of Ni(dcpe)(κ2-S2CNPh), including a single-crystal X-ray structure determination, was achieved.
doi_str_mv	10.1021/acs.organomet.2c00435
format	Article
fullrecord	<record><control><sourceid>acs_osti_</sourceid><recordid>TN_cdi_osti_scitechconnect_1897340</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>f67269459</sourcerecordid><originalsourceid>FETCH-LOGICAL-a369t-6857681fd5e8dc0f3b9adfdada0634cfbd3f8c3d267625b31a67484867fddeef3</originalsourceid><addsrcrecordid>eNqFkMtKAzEUhoMoWKuPIAT3U3OZSdKlFC-Fiop1HdJcOinTpCQR6dub0uLW1Tmc__vP4gPgFqMJRgTfK50nMa1ViFtbJkQj1NLuDIxwR1DDUIvPwQgRzhpOKb0EVzlvEEKMUzICH8ukdjsf1jA6qOBCFdu82qIGuLRp60NdPr8H502E81DqyRpfGfjjSw_fexv2A5znWHof9V6FGl2DC6eGbG9Ocwy-nh6Xs5dm8fY8nz0sGkXZtDRMdJwJ7ExnhdHI0dVUGWeUUYjRVruVoU5oagjjjHQrihXjrWgF484Yax0dg7vj35iLl1n7YnWvYwhWF4nFlNMWVag7QjrFnJN1cpf8VqW9xEge5MkqT_7Jkyd5tYePvUO8id-pisj_dH4BUfl45Q</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Trapping of a Late-Metal Terminal Sulfido Intermediate with Phenyl Isothiocyanate</title><source>ACS Publications</source><creator>Shanahan, James P. ; Vicic, David A. ; Brennessel, William W. ; Jones, William D.</creator><creatorcontrib>Shanahan, James P. ; Vicic, David A. ; Brennessel, William W. ; Jones, William D. ; Univ. of Rochester, NY (United States)</creatorcontrib><description>Nickel–sulfur bonds play key roles in catalysis and biological systems. In most metal complexes, sulfur acts as a bridge joining metal centers, rather than as a terminal sulfide ligand. The addition of phenyl isothiocyanate to Ni(dcpe)(Ph)(SH) afforded the dithiocarbamate complex Ni(dcpe)(κ2-S2CNPh) with the loss of benzene. The reaction was monitored by UV–visible spectroscopy under pseudo-first-order rate conditions and showed limited dependence on isothiocyanate concentration, suggesting that the reaction proceeds through an intermediate terminal sulfido nickel complex. The values of ΔH ⧧ and ΔS ⧧ for the reaction were found to be 18.6 ± 1.5 kcal/mol and −17.8 ± 4.7 eu, respectively. Full characterization of Ni(dcpe)(κ2-S2CNPh), including a single-crystal X-ray structure determination, was achieved.</description><identifier>ISSN: 0276-7333</identifier><identifier>EISSN: 1520-6041</identifier><identifier>DOI: 10.1021/acs.organomet.2c00435</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Chemical reactions ; Kinetics ; Ligands ; Organic reactions ; Phenyls</subject><ispartof>Organometallics, 2022-11, Vol.41 (22), p.3448-3453</ispartof><rights>2022 The Authors. Published by American Chemical Society</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a369t-6857681fd5e8dc0f3b9adfdada0634cfbd3f8c3d267625b31a67484867fddeef3</citedby><cites>FETCH-LOGICAL-a369t-6857681fd5e8dc0f3b9adfdada0634cfbd3f8c3d267625b31a67484867fddeef3</cites><orcidid>0000-0002-4990-0355 ; 0000-0001-5461-1825 ; 0000-0003-1932-0963 ; 0000000319320963 ; 0000000154611825 ; 0000000249900355</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/acs.organomet.2c00435$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/acs.organomet.2c00435$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>230,314,776,780,881,2751,27055,27903,27904,56716,56766</link.rule.ids><backlink>$$Uhttps://www.osti.gov/biblio/1897340$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Shanahan, James P.</creatorcontrib><creatorcontrib>Vicic, David A.</creatorcontrib><creatorcontrib>Brennessel, William W.</creatorcontrib><creatorcontrib>Jones, William D.</creatorcontrib><creatorcontrib>Univ. of Rochester, NY (United States)</creatorcontrib><title>Trapping of a Late-Metal Terminal Sulfido Intermediate with Phenyl Isothiocyanate</title><title>Organometallics</title><addtitle>Organometallics</addtitle><description>Nickel–sulfur bonds play key roles in catalysis and biological systems. In most metal complexes, sulfur acts as a bridge joining metal centers, rather than as a terminal sulfide ligand. The addition of phenyl isothiocyanate to Ni(dcpe)(Ph)(SH) afforded the dithiocarbamate complex Ni(dcpe)(κ2-S2CNPh) with the loss of benzene. The reaction was monitored by UV–visible spectroscopy under pseudo-first-order rate conditions and showed limited dependence on isothiocyanate concentration, suggesting that the reaction proceeds through an intermediate terminal sulfido nickel complex. The values of ΔH ⧧ and ΔS ⧧ for the reaction were found to be 18.6 ± 1.5 kcal/mol and −17.8 ± 4.7 eu, respectively. Full characterization of Ni(dcpe)(κ2-S2CNPh), including a single-crystal X-ray structure determination, was achieved.</description><subject>Chemical reactions</subject><subject>Kinetics</subject><subject>Ligands</subject><subject>Organic reactions</subject><subject>Phenyls</subject><issn>0276-7333</issn><issn>1520-6041</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><recordid>eNqFkMtKAzEUhoMoWKuPIAT3U3OZSdKlFC-Fiop1HdJcOinTpCQR6dub0uLW1Tmc__vP4gPgFqMJRgTfK50nMa1ViFtbJkQj1NLuDIxwR1DDUIvPwQgRzhpOKb0EVzlvEEKMUzICH8ukdjsf1jA6qOBCFdu82qIGuLRp60NdPr8H502E81DqyRpfGfjjSw_fexv2A5znWHof9V6FGl2DC6eGbG9Ocwy-nh6Xs5dm8fY8nz0sGkXZtDRMdJwJ7ExnhdHI0dVUGWeUUYjRVruVoU5oagjjjHQrihXjrWgF484Yax0dg7vj35iLl1n7YnWvYwhWF4nFlNMWVag7QjrFnJN1cpf8VqW9xEge5MkqT_7Jkyd5tYePvUO8id-pisj_dH4BUfl45Q</recordid><startdate>20221128</startdate><enddate>20221128</enddate><creator>Shanahan, James P.</creator><creator>Vicic, David A.</creator><creator>Brennessel, William W.</creator><creator>Jones, William D.</creator><general>American Chemical Society</general><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope><orcidid>https://orcid.org/0000-0002-4990-0355</orcidid><orcidid>https://orcid.org/0000-0001-5461-1825</orcidid><orcidid>https://orcid.org/0000-0003-1932-0963</orcidid><orcidid>https://orcid.org/0000000319320963</orcidid><orcidid>https://orcid.org/0000000154611825</orcidid><orcidid>https://orcid.org/0000000249900355</orcidid></search><sort><creationdate>20221128</creationdate><title>Trapping of a Late-Metal Terminal Sulfido Intermediate with Phenyl Isothiocyanate</title><author>Shanahan, James P. ; Vicic, David A. ; Brennessel, William W. ; Jones, William D.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a369t-6857681fd5e8dc0f3b9adfdada0634cfbd3f8c3d267625b31a67484867fddeef3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>Chemical reactions</topic><topic>Kinetics</topic><topic>Ligands</topic><topic>Organic reactions</topic><topic>Phenyls</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Shanahan, James P.</creatorcontrib><creatorcontrib>Vicic, David A.</creatorcontrib><creatorcontrib>Brennessel, William W.</creatorcontrib><creatorcontrib>Jones, William D.</creatorcontrib><creatorcontrib>Univ. of Rochester, NY (United States)</creatorcontrib><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>Organometallics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Shanahan, James P.</au><au>Vicic, David A.</au><au>Brennessel, William W.</au><au>Jones, William D.</au><aucorp>Univ. of Rochester, NY (United States)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Trapping of a Late-Metal Terminal Sulfido Intermediate with Phenyl Isothiocyanate</atitle><jtitle>Organometallics</jtitle><addtitle>Organometallics</addtitle><date>2022-11-28</date><risdate>2022</risdate><volume>41</volume><issue>22</issue><spage>3448</spage><epage>3453</epage><pages>3448-3453</pages><issn>0276-7333</issn><eissn>1520-6041</eissn><abstract>Nickel–sulfur bonds play key roles in catalysis and biological systems. In most metal complexes, sulfur acts as a bridge joining metal centers, rather than as a terminal sulfide ligand. The addition of phenyl isothiocyanate to Ni(dcpe)(Ph)(SH) afforded the dithiocarbamate complex Ni(dcpe)(κ2-S2CNPh) with the loss of benzene. The reaction was monitored by UV–visible spectroscopy under pseudo-first-order rate conditions and showed limited dependence on isothiocyanate concentration, suggesting that the reaction proceeds through an intermediate terminal sulfido nickel complex. The values of ΔH ⧧ and ΔS ⧧ for the reaction were found to be 18.6 ± 1.5 kcal/mol and −17.8 ± 4.7 eu, respectively. Full characterization of Ni(dcpe)(κ2-S2CNPh), including a single-crystal X-ray structure determination, was achieved.</abstract><cop>United States</cop><pub>American Chemical Society</pub><doi>10.1021/acs.organomet.2c00435</doi><tpages>6</tpages><orcidid>https://orcid.org/0000-0002-4990-0355</orcidid><orcidid>https://orcid.org/0000-0001-5461-1825</orcidid><orcidid>https://orcid.org/0000-0003-1932-0963</orcidid><orcidid>https://orcid.org/0000000319320963</orcidid><orcidid>https://orcid.org/0000000154611825</orcidid><orcidid>https://orcid.org/0000000249900355</orcidid><oa>free_for_read</oa></addata></record>
fulltext	fulltext
identifier	ISSN: 0276-7333
ispartof	Organometallics, 2022-11, Vol.41 (22), p.3448-3453
issn	0276-7333 1520-6041
language	eng
recordid	cdi_osti_scitechconnect_1897340
source	ACS Publications
subjects	Chemical reactions Kinetics Ligands Organic reactions Phenyls
title	Trapping of a Late-Metal Terminal Sulfido Intermediate with Phenyl Isothiocyanate
url	https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-25T12%3A26%3A46IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-acs_osti_&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Trapping%20of%20a%20Late-Metal%20Terminal%20Sulfido%20Intermediate%20with%20Phenyl%20Isothiocyanate&rft.jtitle=Organometallics&rft.au=Shanahan,%20James%20P.&rft.aucorp=Univ.%20of%20Rochester,%20NY%20(United%20States)&rft.date=2022-11-28&rft.volume=41&rft.issue=22&rft.spage=3448&rft.epage=3453&rft.pages=3448-3453&rft.issn=0276-7333&rft.eissn=1520-6041&rft_id=info:doi/10.1021/acs.organomet.2c00435&rft_dat=%3Cacs_osti_%3Ef67269459%3C/acs_osti_%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_id=info:pmid/&rfr_iscdi=true