Synthesis and reactivity of Pd(II) imidoyl complexes obtained by insertion of isocyanoferrocene into the Pd–C bonds of orthopalladated precursors
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F23%3A10472800" target="_blank" >RIV/00216208:11310/23:10472800 - isvavai.cz</a>
Result on the web
<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=3xRB2SMaqE" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=3xRB2SMaqE</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/d3dt02717a" target="_blank" >10.1039/d3dt02717a</a>
Alternative languages
Result language
angličtina
Original language name
Synthesis and reactivity of Pd(II) imidoyl complexes obtained by insertion of isocyanoferrocene into the Pd–C bonds of orthopalladated precursors
Original language description
While the multifaceted reactivity of organic isocyanides has been extensively demonstrated, that of their organometallic analogue, isocyanoferrocene (FcNC; Fc = ferrocenyl), has not yet been adequately explored. This contribution describes the syntheses of novel chelating Pd(II) imidoyl complexes, [(YCH2C6H4C(NFc)-κ(2)Y,C)PdCl(PR3)], by insertion of FcNC into the Pd-C bond of cyclopalladated precursors [(YCH2C6H4-κ(2)Y,C)PdCl(PR3)] (Y = Me2N, MeS, R = Ph, Me). The imidoyl complexes underwent facile alkylation with [Me3O][BF4] to produce the cationic aminocarbene complexes [{YCH2C6H4C(N(Me)Fc)-κ(2)Y,C}PdCl(PR3)][BF4]. All compounds were fully characterised using a combination of spectroscopic methods (NMR, FTIR and ESI MS), cyclic voltammetry and single-crystal X-ray crystallography. In addition, DFT calculations were used to describe the bonding in the two compound families. Analyses with intrinsic bond orbitals (IBOs) and the quantum theory of atoms in molecules (QTAIM) consistently pointed to the transformation of an X-type imidoyl C-ligand (sigma-organyl) into an L-type carbene donor upon alkylation, which has only a minor structural consequence. Also reported is the unexpected conversion of the imidoyl complex [(Me2NCH2C6H4C(NFc)-κ(2)N,C)PdCl(PPh3)] into (Z)-2,2-dimethyl-1-(ferrocenylimino)isoindolin-2-ium tetrafluoroborate as a reductive elimination product, which was induced by Lewis and Bronsted acids.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10402 - Inorganic and nuclear chemistry
Result continuities
Project
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Continuities
S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Dalton Transactions
ISSN
1477-9226
e-ISSN
1477-9234
Volume of the periodical
52
Issue of the periodical within the volume
47
Country of publishing house
GB - UNITED KINGDOM
Number of pages
10
Pages from-to
17701-17710
UT code for WoS article
001085539700001
EID of the result in the Scopus database
2-s2.0-85174530268