The missing entry in the agostic-anagostic series: Rh(I)-1-c interactions in P(Ch)p pincer complexes
dc.contributor.author
dc.date.accessioned
2015-10-20T13:57:24Z
dc.date.available
2015-10-20T13:57:24Z
dc.date.issued
2015-03-16
dc.identifier.issn
0020-1669
dc.identifier.uri
dc.description.abstract
The missing entry, namely, the "C-anagostic" or δ1-C interaction, closing the agostic-anagostic series of metal-CH(aryl) interactions is found in a bis(amidiniophosphine) P(CH)P pincer rhodium complex. The three entries, namely, agostic δ2-(C,H), anagostic (related to hydrogen bonding, thus recoined here as "H-anagostic"), and C-anagostic interactions, are unambiguously characterized by electron localization function (ELF) topological analysis. Other theoretical tools such as noncovalent interaction (NCI) analysis and multicenter electron delocalization indices (MCIs) support the ELF characterization. A δ2-(C,H) agostic interaction is evidenced by a disynaptic V(C,H) or trisynaptic V(M,C,H) ELF basin with a significant quantum topological atoms in molecules (QTAIM) atomic contribution of the metal M and a large covariance (in absolute value) with the metal core basin C(M). The C-anagostic δ1-C interaction is characterized by a disynaptic V(M,C) basin, a weak covariance (in absolute value) of V(C,H) and C(M) populations, and a negligible QTAIM atomic contribution of M to V(C,H). The relevance of these ELF signatures is evidenced in a selected series of related rhodium and osmium complexes
dc.description.sponsorship
The theoretical studies were performed using HPC resources from CALMIP (Grant 2011-2013[0851]) and from GENCI-[CINES/IDRIS] (Grant 2011-2013[085008]). J.P. and M.S. are grateful to the following organizations for financial support: the Ministerio de Ciencia e Innovacion (Projects CTQ2011-23156/BQU and CTQ2011-25086/BQU) and the Generalitat de Catalunya (Projects 2014SGR931, 2009SGR528, and 2009SGR637; AIRE-CTP2012 fellowship for J.P.; 2014 ICREA Academia prize for excellence in research funded by the DIUE for M.S.)
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
dc.relation
info:eu-repo/grantAgreement/MICINN//CTQ2011-23156/ES/AVANCES EN CATALISIS Y AROMATICIDAD/
info:eu-repo/grantAgreement/MICINN//CTQ2011-25086/ES/MODELIZACION MULTIESCALAR EN (BIO)QUIMICA/
AGAUR/2014-2016/2014 SGR-931
AGAUR/2009-2014/2009 SGR-528
AGAUR/2009-2014/2009 SGR-637
dc.relation.isformatof
Reproducció digital del document publicat a: http://dx.doi.org/10.1021/acs.inorgchem.5b00069
dc.relation.ispartof
© Inorganic Chemistry, 2015, vol. 54, núm. 6, p. 2960-2969
dc.relation.ispartofseries
Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.title
The missing entry in the agostic-anagostic series: Rh(I)-1-c interactions in P(Ch)p pincer complexes
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/embargoedAccess
dc.embargo.terms
Cap
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
023601
dc.contributor.funder
dc.relation.ProjectAcronym
dc.identifier.eissn
1520-510X