N[sbnd]o bond cleavage and n2 activation reactions of the nitrosyl-bridged complex [mo2cp2(µ-ptbu2)(µ-no)(no)2]

The title compound was prepared through a three-step procedure starting with the hydride complex [Mo2Cp2(µH)(µ-Pt Bu2)(CO)4], which was first dehydrogenated through reaction with HBF4⋅OEt2 to give the unsaturated complex [Mo2Cp2(µ-Pt Bu2)(CO)4](BF4) (Mo=Mo), which displays a transoid structure accor...

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Autores: Álvarez Fidalgo, María Ángeles|||0000-0002-3313-1467, García Díaz, María Esther|||0000-0002-9185-0099, García Vivó, Daniel, Guerra Muñiz, Ana María, Ruiz Álvarez, Miguel Ángel|||0000-0002-9016-4046
Tipo de recurso: artículo
Fecha de publicación:2024
País:España
Institución:Universidad de Oviedo (UNIOVI)
Repositorio:RUO. Repositorio Institucional de la Universidad de Oviedo
Idioma:inglés
OAI Identifier:oai:digibuo.uniovi.es:10651/76925
Acceso en línea:https://hdl.handle.net/10651/76925
https://dx.doi.org/10.1016/j.jorganchem.2024.123375
Access Level:acceso abierto
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spelling N[sbnd]o bond cleavage and n2 activation reactions of the nitrosyl-bridged complex [mo2cp2(µ-ptbu2)(µ-no)(no)2]Álvarez Fidalgo, María Ángeles|||0000-0002-3313-1467García Díaz, María Esther|||0000-0002-9185-0099García Vivó, DanielGuerra Muñiz, Ana MaríaRuiz Álvarez, Miguel Ángel|||0000-0002-9016-4046The title compound was prepared through a three-step procedure starting with the hydride complex [Mo2Cp2(µH)(µ-Pt Bu2)(CO)4], which was first dehydrogenated through reaction with HBF4⋅OEt2 to give the unsaturated complex [Mo2Cp2(µ-Pt Bu2)(CO)4](BF4) (Mo=Mo), which displays a transoid structure according to experimental (Mo-Mo = 2.8283(7) Å) and Density Functional Theory studies. The latter was then reacted with NO to give the dinitrosyl derivative [Mo2Cp2(µ-Pt Bu2)(CO)2(NO)2](BF4), which in turn was further decarbonylated and nitrosylated upon reaction with [N(PPh3)2]NO2 to give the title nitrosyl-bridged complex (Mo-Mo = 2.905(1) Å). This complex displayed a structure comparable to that of its PCy2-bridged analogue, with similar pyramidalization of the bridging nitrosyl, but a more pronounced folding of the central MoPMoN skeleton and bending of terminal nitrosyls. It also displayed a similar N–O bond activation chemistry, as shown by its reactions with HBF4⋅OEt2 to give the nitroxyl-bridged complex [Mo2Cp2(µ-Pt Bu2)(µ-k1 :η2 -HNO)(NO)2](BF4) (HN–O = 1.330(8) Å), with P (OEt)3 to give the phosphoraniminate-bridged complex [Mo2Cp2(µ-Pt Bu2){µ-NP(OEt)3}(NO)2], and with Na(Hg) to give the amide-bridged derivative [Mo2Cp2(µ-Pt Bu2)(µ-NH2)(NO)2]. Under a nitrogen atmosphere, however, the latter reaction also gave a minor side product identified as the dinitrogen-bridged derivative [Mo4Cp4(µPt Bu2)2(µ4-N2)(NO)4]. This tetranuclear complex displays a dinitrogen molecule bridging four metal atoms in the novel µ4-k1 :k1 :k1 :k1 coordination mode, with strong metal-nitrogen interactions taking the N2 ligand to the diazendiide (N2 2-) limit (N–N = 1.241(3) Å).MICIU; AEI of Spain; FEDER [PGC2021-123964NB-I00]20242024-01-01journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articlehttps://hdl.handle.net/10651/76925https://dx.doi.org/10.1016/j.jorganchem.2024.123375Scopushttps://www.scopus.com/inward/record.uri?eid=2-s2.0-85204370244&doi=10.1016%2fj.jorganchem.2024.123375&partnerID=40&md5=7af3ccb2854781ac8f88164ddd0fbaeereponame:RUO. Repositorio Institucional de la Universidad de Oviedoinstname:Universidad de Oviedo (UNIOVI)Inglésengopen accesshttp://purl.org/coar/access_right/c_abf2Attribution-NonCommercial-NoDerivatives 4.0 Internationalhttp://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccessoai:digibuo.uniovi.es:10651/769252026-06-07T06:38:51Z
dc.title.none.fl_str_mv N[sbnd]o bond cleavage and n2 activation reactions of the nitrosyl-bridged complex [mo2cp2(µ-ptbu2)(µ-no)(no)2]
title N[sbnd]o bond cleavage and n2 activation reactions of the nitrosyl-bridged complex [mo2cp2(µ-ptbu2)(µ-no)(no)2]
spellingShingle N[sbnd]o bond cleavage and n2 activation reactions of the nitrosyl-bridged complex [mo2cp2(µ-ptbu2)(µ-no)(no)2]
Álvarez Fidalgo, María Ángeles|||0000-0002-3313-1467
title_short N[sbnd]o bond cleavage and n2 activation reactions of the nitrosyl-bridged complex [mo2cp2(µ-ptbu2)(µ-no)(no)2]
title_full N[sbnd]o bond cleavage and n2 activation reactions of the nitrosyl-bridged complex [mo2cp2(µ-ptbu2)(µ-no)(no)2]
title_fullStr N[sbnd]o bond cleavage and n2 activation reactions of the nitrosyl-bridged complex [mo2cp2(µ-ptbu2)(µ-no)(no)2]
title_full_unstemmed N[sbnd]o bond cleavage and n2 activation reactions of the nitrosyl-bridged complex [mo2cp2(µ-ptbu2)(µ-no)(no)2]
title_sort N[sbnd]o bond cleavage and n2 activation reactions of the nitrosyl-bridged complex [mo2cp2(µ-ptbu2)(µ-no)(no)2]
dc.creator.none.fl_str_mv Álvarez Fidalgo, María Ángeles|||0000-0002-3313-1467
García Díaz, María Esther|||0000-0002-9185-0099
García Vivó, Daniel
Guerra Muñiz, Ana María
Ruiz Álvarez, Miguel Ángel|||0000-0002-9016-4046
author Álvarez Fidalgo, María Ángeles|||0000-0002-3313-1467
author_facet Álvarez Fidalgo, María Ángeles|||0000-0002-3313-1467
García Díaz, María Esther|||0000-0002-9185-0099
García Vivó, Daniel
Guerra Muñiz, Ana María
Ruiz Álvarez, Miguel Ángel|||0000-0002-9016-4046
author_role author
author2 García Díaz, María Esther|||0000-0002-9185-0099
García Vivó, Daniel
Guerra Muñiz, Ana María
Ruiz Álvarez, Miguel Ángel|||0000-0002-9016-4046
author2_role author
author
author
author
description The title compound was prepared through a three-step procedure starting with the hydride complex [Mo2Cp2(µH)(µ-Pt Bu2)(CO)4], which was first dehydrogenated through reaction with HBF4⋅OEt2 to give the unsaturated complex [Mo2Cp2(µ-Pt Bu2)(CO)4](BF4) (Mo=Mo), which displays a transoid structure according to experimental (Mo-Mo = 2.8283(7) Å) and Density Functional Theory studies. The latter was then reacted with NO to give the dinitrosyl derivative [Mo2Cp2(µ-Pt Bu2)(CO)2(NO)2](BF4), which in turn was further decarbonylated and nitrosylated upon reaction with [N(PPh3)2]NO2 to give the title nitrosyl-bridged complex (Mo-Mo = 2.905(1) Å). This complex displayed a structure comparable to that of its PCy2-bridged analogue, with similar pyramidalization of the bridging nitrosyl, but a more pronounced folding of the central MoPMoN skeleton and bending of terminal nitrosyls. It also displayed a similar N–O bond activation chemistry, as shown by its reactions with HBF4⋅OEt2 to give the nitroxyl-bridged complex [Mo2Cp2(µ-Pt Bu2)(µ-k1 :η2 -HNO)(NO)2](BF4) (HN–O = 1.330(8) Å), with P (OEt)3 to give the phosphoraniminate-bridged complex [Mo2Cp2(µ-Pt Bu2){µ-NP(OEt)3}(NO)2], and with Na(Hg) to give the amide-bridged derivative [Mo2Cp2(µ-Pt Bu2)(µ-NH2)(NO)2]. Under a nitrogen atmosphere, however, the latter reaction also gave a minor side product identified as the dinitrogen-bridged derivative [Mo4Cp4(µPt Bu2)2(µ4-N2)(NO)4]. This tetranuclear complex displays a dinitrogen molecule bridging four metal atoms in the novel µ4-k1 :k1 :k1 :k1 coordination mode, with strong metal-nitrogen interactions taking the N2 ligand to the diazendiide (N2 2-) limit (N–N = 1.241(3) Å).
publishDate 2024
dc.date.none.fl_str_mv 2024
2024-01-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://hdl.handle.net/10651/76925
https://dx.doi.org/10.1016/j.jorganchem.2024.123375
url https://hdl.handle.net/10651/76925
https://dx.doi.org/10.1016/j.jorganchem.2024.123375
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Attribution-NonCommercial-NoDerivatives 4.0 International
http://creativecommons.org/licenses/by-nc-nd/4.0/
eu_rights_str_mv openAccess
dc.source.none.fl_str_mv Scopus
https://www.scopus.com/inward/record.uri?eid=2-s2.0-85204370244&doi=10.1016%2fj.jorganchem.2024.123375&partnerID=40&md5=7af3ccb2854781ac8f88164ddd0fbaee
reponame:RUO. Repositorio Institucional de la Universidad de Oviedo
instname:Universidad de Oviedo (UNIOVI)
instname_str Universidad de Oviedo (UNIOVI)
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