On the role of the imide axial ligand in the spin and oxidation state of Mn corrole and corrolazine complexes

Rosa Caballol; Gerard Alcover; Kristin Pierloot; Coen de Graaf

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On the role of the imide axial ligand in the spin and oxidation state of Mn corrole and corrolazine complexes - PC:1524

Handle:

https://hdl.handle.net/20.500.11797/PC1524

Autor/es de la URV:	CABALLOL LORENZO, ROSA; Gerard Alcover; Kristin Pierloot; DE GRAAF ., CORNELIS
Autor según el artículo:	Rosa Caballol; Gerard Alcover; Kristin Pierloot; Coen de Graaf
Identificador del autor:	n/a; n/a; n/a; 0000-0001-8114-6658
Año de publicación de la revista:	2016
Tipo de publicación:	Artículo
ISSN:	0020-1669
DOI del artículo:	10.1021/acs.inorgchem.6b00194
Enlace a la fuente original:	https://pubs.acs.org/doi/10.1021/acs.inorgchem.6b00194
Versión del articulo depositado:	info:eu-repo/semantics/acceptedVersion
Acceso a la licencia de uso:	https://creativecommons.org/licenses/by/3.0/es/
Departamento:	Química Física i Inorgànica
Grupo de investigación:	Química Quàntica
URL Documento de licencia:	https://repositori.urv.cat/ca/proteccio-de-dades/
Áreas temáticas:	Química
Entidad:	Universitat Rovira i Virgili
Fecha de alta del registro:	2016-04-28

Descripción:	Electronic structure calculations have been performed on four different Mn corrole and corrolazine complexes to clarify the role of the imide axial ligand on the relative stability of the different spin states and the stabilization of the high valent Mn ion in these complexes. Multiconfigurational perturbation theory energy calculations on the DFT optimized geometries shows that all complexes have a singlet ground state except the complex with the strongest electron withdrawing substituent on the imide axial ligand, which is found to have a triplet ground state. The analysis of the sigma and pi interaction between metal and imide ligand shows that this spin crossover is caused by a subtle interplay of geometrical factors (Mn-N distance and coordination angle) and the electron withdrawing character of the substituent on the imide, which reduces the electron donation to the metal centre. The analysis of the multiconfigurational wave functions reveals that the formally MnV ion is stabilized by an important electron transfer from both the equatorial corrole/corrolazine ligand and the axial imide. The macrocycle donates roughly half an electron, being somewhere between the closed-shell trianionic and the dianionic radical form. The imide ligand transfers 2.5 electrons to the metal center, resulting in an effective d-electron count close to five in all complexes.
Cobertura:	Anglès
Tipo:	post-print Article Artículo Article info:eu-repo/semantics/acceptedVersion
Coautor:	Química Quàntica Química Física i Inorgànica Universitat Rovira i Virgili
Títol:	On the role of the imide axial ligand in the spin and oxidation state of Mn corrole and corrolazine complexes
Materia:	Complexos metàl·lics de transició Estructura electrònica Química inorgànica transition-metal complexes electronic structure Inorganic Chemistry Chemistry Química Química 0020-1669
Fecha:	2016
Formato:	1520 kb
Autor:	Rosa Caballol Gerard Alcover Kristin Pierloot Coen de Graaf
Derechos:	info:eu-repo/semantics/openAccess

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