<div class="csl-bib-body">
<div class="csl-entry">Mota Merelo de Aguiar, S. R., Stöger, B., Pittenauer, E., Allmaier, G., Veiros, L. F., & Kirchner, K. (2016). Structural diversity of halocarbonyl molybdenum and tungsten PNP pincer complexes through ligand modifications. <i>Dalton Transactions</i>, <i>45</i>, 13834–13845. https://doi.org/10.1039/C6DT02251K</div>
</div>
-
dc.identifier.issn
1477-9226
-
dc.identifier.uri
http://hdl.handle.net/20.500.12708/20214
-
dc.description.abstract
This work presents a comparative study of a series of halocarbonyl Mo(II) and W(II) complexes of the types [M(PNP)(CO)3X]X and [M(PNP)(CO)2X2] (M = Mo, W; X = I, Br), featuring PNP pincer ligands based on a 2,6-diaminopyridine scaffold. The complexes were prepared and fully characterized. The syntheses of these complexes were accomplished by treatment of [M(PNP)(CO)3] with stoichiometric amounts of I2 and Br2, respectively. The modification of the 2,6-diaminopyridine scaffold by introducing NMe and NPh instead of NH spacers with concomitant modification of the phosphine moieties changed the steric and electronic properties of the PNP ligand significantly. While in the case of NH linkers exclusively cationic seven-coordinate complexes of the type [M(PNP)(CO)3X]+ were obtained with NMe and NPh spacers neutral seven-coordinate complexes of the type [M(PNP)(CO)2X2] were afforded. In the case of the latter, when the reaction is performed in the presence of CO also [M(PNP)(CO)3X]+ complexes are formed which slowly lose CO to give [M(PNP)(CO)2X2]. The halocarbonyl tungsten chemistry parallels that of molybdenum. The only exception is molybdenum in conjunction with the PNPMe-iPr ligand, where the coordinatively unsaturated complex [Mo(PNPMe-iPr)(CO)X2] is formed. DFT mechanistic studies reveal that the seven-coordinate complexes should be the thermodynamic as well as the kinetic products. Since [Mo(PNPMe-iPr)(CO)X2] is the observed product it suggests that the reaction follows an alternative path. Structures of representative complexes were determined by X-ray single crystal analyses.
en
dc.language.iso
en
-
dc.publisher
ROYAL SOC CHEMISTRY
-
dc.relation.ispartof
Dalton Transactions
-
dc.rights.uri
http://creativecommons.org/licenses/by/3.0/
-
dc.subject
PNP
en
dc.title
Structural diversity of halocarbonyl molybdenum and tungsten PNP pincer complexes through ligand modifications
en
dc.type
Article
en
dc.type
Artikel
de
dc.rights.license
Creative Commons Attribution 3.0 Unported
en
dc.rights.license
Creative Commons Namensnennung 3.0 Unported
de
dc.contributor.affiliation
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa
-
dc.description.startpage
13834
-
dc.description.endpage
13845
-
dcterms.dateSubmitted
2016-06-06
-
dc.type.category
Original Research Article
-
tuw.container.volume
45
-
tuw.journal.peerreviewed
true
-
tuw.peerreviewed
true
-
wb.publication.intCoWork
International Co-publication
-
dcterms.isPartOf.title
Dalton Transactions
-
tuw.publication.orgunit
E163-01 - Forschungsbereich Anorganische Chemie
-
tuw.publisher.doi
10.1039/C6DT02251K
-
dc.identifier.eissn
1477-9234
-
dc.identifier.libraryid
AC17204922
-
dc.description.numberOfPages
12
-
tuw.author.orcid
0000-0002-0087-474X
-
tuw.author.orcid
0000-0002-8409-802X
-
tuw.author.orcid
0000-0002-1438-9462
-
tuw.author.orcid
0000-0001-5841-3519
-
tuw.author.orcid
0000-0003-0872-6159
-
dc.rights.identifier
CC BY 3.0
en
dc.rights.identifier
CC BY 3.0
de
wb.sci
true
-
item.mimetype
application/pdf
-
item.openairetype
research article
-
item.openairecristype
http://purl.org/coar/resource_type/c_2df8fbb1
-
item.openaccessfulltext
Open Access
-
item.grantfulltext
open
-
item.cerifentitytype
Publications
-
item.fulltext
with Fulltext
-
item.languageiso639-1
en
-
crisitem.author.dept
E163 - Institut für Angewandte Synthesechemie
-
crisitem.author.dept
E057-04 - Fachbereich Röntgenzentrum
-
crisitem.author.dept
E164-01-1 - Forschungsgruppe Massenspektrometrische Bio- und Polymeranalytik
-
crisitem.author.dept
E164-01-1 - Forschungsgruppe Massenspektrometrische Bio- und Polymeranalytik
-
crisitem.author.dept
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa
-
crisitem.author.dept
E163-01 - Forschungsbereich Anorganische Chemie
-
crisitem.author.orcid
0000-0002-0087-474X
-
crisitem.author.orcid
0000-0002-8409-802X
-
crisitem.author.orcid
0000-0002-1438-9462
-
crisitem.author.orcid
0000-0001-5841-3519
-
crisitem.author.orcid
0000-0003-0872-6159
-
crisitem.author.parentorg
E150 - Fakultät für Technische Chemie
-
crisitem.author.parentorg
E057 - Facilities und Zentren
-
crisitem.author.parentorg
E164-01 - Forschungsbereich Imaging und Instrumentelle Analytische Chemie
-
crisitem.author.parentorg
E164-01 - Forschungsbereich Imaging und Instrumentelle Analytische Chemie