Experimental and computational tuning of metalla-N-heterocyclic carbenes at palladium(<scp>ii</scp>) and platinum(<scp>ii</scp>) centers

Kashina, Maria V.; Luzyanin, Konstantin V.; Катленок, Е. А.; Novikov, Alexander S.; Kinzhalov, Mikhail A.

doi:10.1039/d2dt00252c

Cited by 17 publications

(9 citation statements)

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“…The palladium(II) and platinum(II) coordination centers exhibit a distorted square-planar geometry; the M–N bond lengths and the angles agree well with the data for relevant platinum and palladium thiocyanate complexes from our Cambridge Structural Database (CSD) search (Section ). The angles ∠M 2 –N 9 –C 42 (171.50(17), 174.1(2)°) are almost linear, and their values agree well with the reported data ,, for relevant platinum and palladium complexes featuring thiocyanate ligands and the CSD search performed in our previous work …”

Section: Results and Discussionsupporting

confidence: 89%

“…On the first step, the organometallic skeletons in 1 and 2 were constructed by the nucleophilic addition of 2aminopyrazine to the metal-activated isocyanide ligands in cis-[MCl 2 (CNXyl) 2 ] (M = Pd, Pt); this coupling occurred similar to the reported reactions of various aminoheterocycles. 68,69 The authenticity of 1 was proved by comparison of their 1 H NMR data with the previously reported spectra, 70 while the composition and structure of the newly obtained complex 2 was confirmed by microanalyses and spectroscopic methods and also by a single-crystal X-ray diffraction study (for details, see the Supporting Information, Section S2).…”

Section: Resultsmentioning

confidence: 64%

“…The binuclear thiocyanate complexes were prepared by a two-step procedure (Scheme ). On the first step, the organometallic skeletons in 1 and 2 were constructed by the nucleophilic addition of 2-aminopyrazine to the metal-activated isocyanide ligands in cis -[MCl 2 (CNXyl) 2 ] (M = Pd, Pt); this coupling occurred similar to the reported reactions of various aminoheterocycles. , …”

Section: Results and Discussionmentioning

confidence: 82%

“…In view of our ,, and other groups ,, interest in noncovalent bonding patterns of metal coordinated thiocyanates, in this study, we analyzed M···SCN–M′ contacts and classified them as linear and bent (Figure ). The results of our CSD search indicate that, in the overwhelming majority of the reported structures, ∠MSC of M···SCN–M′ short separations are spanning the range between 80 and 120° (Figure B).…”

Section: Discussionmentioning

confidence: 99%

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Linear and Bent Noncovalent M···S═C═N–M′ Interactions: The Case of Palladium(II) and Platinum(II) Thiocyanate Species

Kashina

Kinzhalov

Tupikina

et al. 2023

Crystal Growth & Design

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Analysis of X-ray crystal structures of newly prepared thiocyanate PdII and PtII complexes revealed the bifurcated (M–N)···S contacts in which angles ∠M···SC are close to 180°. All M···SCN–M′ noncovalent interactionsidentified in this study and also those found on the Cambridge Structural Database searchwere systematized as linear (approximately 180°) and bent (∠M···SC 80–120°). Results of appropriate theoretical study indicate that, although the linear configuration of the PdII and PtII structures is primarily determined by crystal packing effects, the attractive M···S forces are far from negligible and the linear structures correspond to the energy minimum. Furthermore, the linear arrangement is mostly determined by orbital interactions, while the bent configuration by electrostatic forces. Molecular electrostatic potential (MEP) surfaces along with the quantum theory of “atoms-in-molecules” (QTAIM) and the noncovalent interaction plot index (NCIPlot) computational tools were used to characterize the bifurcated (M–N)···S interactions. The nature of the noncovalent M···SCN–M′ forces in the PdII and PtII structures was established by NBO analysis: in both cases, the predominant donor–acceptor orbital interactions include the charge transfer from lone pair orbitals located at the M atom to the σ*-orbital of the S–C bond of a thiocyanate ligand from a neighboring complex.

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Section: Results and Discussionsupporting

confidence: 89%

Section: Resultsmentioning

confidence: 64%

Section: Results and Discussionmentioning

confidence: 82%

Section: Discussionmentioning

confidence: 99%

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Linear and Bent Noncovalent M···S═C═N–M′ Interactions: The Case of Palladium(II) and Platinum(II) Thiocyanate Species

Kashina

Kinzhalov

Tupikina

et al. 2023

Crystal Growth & Design

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“…The UV/vis spectra of 5 – 9 in CH 2 Cl 2 display high-energy intense absorption bands at 250–300 nm assigned to the transitions to ligand-centered states (π–π*), together with less intense bands at 300–400 nm ( Figure S5 ). From the data on related complexes featuring cyclometalated diaminocarbene ligands, 18 these bands can be associated with the transitions to mixed singlet-state ligand-to-ligand charge-transfer ( 1 LL′CT) and singlet-state intraligand charge-transfer ( 1 ILCT) states. It cannot, however, be ruled out that the weak band at 406 nm for the bis(cyclometalated) Pt II complex is due to the direct S 1 → T 1 transition enabled by the large spin–orbit coupling of the Pt center.…”

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confidence: 99%

Phosphorescent Cyclometalated Palladium(II) and Platinum(II) Complexes Derived from Diaminocarbene Precursors

Kashina,

Luzyanin,

Dar’in

et al. 2024

Inorg. Chem.

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Metal-mediated self-assembly of isocyanides and methyl 4-aminopyrimidine-5-carboxylate leads to luminescent Pd II and Pt II complexes featuring C,N-cyclometalated acyclic diaminocarbene (ADC) ligands. The solid-state luminescent properties of these diaminocarbene derivatives are attributed to their triplet-state metal/metal-to-ligand charge-transfer ( 3 MMLCT) nature, which is driven by attractive intermolecular M•••M interactions further reinforced by the intramolecular π−π interactions even in the structure of the Pd compound, which is the first Pd-ADC phosphor reported. C,N-cyclometalated diaminocarbene-based ligands provides access to unique luminescent Pd II derivatives. The emergence of intermolecular interactions is recognized as a driving force toward the phosphorescence of diaminocarbene complexes described in this work, and our future efforts will be dedicated to a better understanding of the relationship between the molecular construction and luminescence properties of metal aminocarbene species. ■ ASSOCIATED CONTENT * sı Supporting InformationThe Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c03346.Experimental section, spectral, XRD, and experimental data, structural features discussion, and theoretical calculations (PDF)Accession Codes

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Four‐Membered Bimetallic Carbon Complex [(M(η⁵‐C₅(CH₃)₅))₂(μ‐NPh)(μ‐C)] (M=Fe, Ru, Os) – An Ambiphilic Carbene with Lone Pair and σ‐Hole Reactivity

Parvathy

Parameswaran

2023

Chemistry A European J

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Singlet carbenes are extensively studied compounds capable of electrophilic, nucleophilic or ambiphilic behaviour. The ambiphilic reactivity of singlet carbenes has been conventionally observed in orthogonal planes. Here, we report a detailed bonding and reactivity study of a homobimetallic carbon complex [(MCp*)2(μ‐NPh)(μ‐C)] (1M, M=Fe, Ru, Os) that shows ambiphilicity in the same direction. The structure of this complex can be considered as two fused three‐membered M−C−M and M−N−M rings. The bonding analysis suggests that these 17 valence electron homobimetallic complexes have one formal M−M bond with a bridging carbene centre featuring a high‐lying spn‐hybridised lone pair. Accordingly, the carbene centre shows high proton affinity and act as a good 2e− donor to Lewis acids and transition metal fragment. Apart from the transition metal non‐bonding electrons, the π‐framework of M−C−M and M−N−M arms can be best described as 3c–2e− bonds. The two transition metals in the four‐membered skeleton generate many low‐lying, virtual orbitals. These low‐lying virtual orbitals induce electron excitation from the spn‐hybrid orbital in presence of H− and other 2e− donor ligands such as PMe3, NHC and CO. Hence, the spn‐hybrid lone pair orbital shows σ‐hole reactivity in presence of Lewis bases.

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Experimental and computational tuning of metalla-N-heterocyclic carbenes at palladium(ii) and platinum(ii) centers

Cited by 17 publications

References 130 publications

Linear and Bent Noncovalent M···S═C═N–M′ Interactions: The Case of Palladium(II) and Platinum(II) Thiocyanate Species

Linear and Bent Noncovalent M···S═C═N–M′ Interactions: The Case of Palladium(II) and Platinum(II) Thiocyanate Species

Phosphorescent Cyclometalated Palladium(II) and Platinum(II) Complexes Derived from Diaminocarbene Precursors

Four‐Membered Bimetallic Carbon Complex [(M(η⁵‐C₅(CH₃)₅))₂(μ‐NPh)(μ‐C)] (M=Fe, Ru, Os) – An Ambiphilic Carbene with Lone Pair and σ‐Hole Reactivity

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Experimental and computational tuning of metalla-N-heterocyclic carbenes at palladium(ii) and platinum(ii) centers

Cited by 17 publications

References 130 publications

Linear and Bent Noncovalent M···S═C═N–M′ Interactions: The Case of Palladium(II) and Platinum(II) Thiocyanate Species

Linear and Bent Noncovalent M···S═C═N–M′ Interactions: The Case of Palladium(II) and Platinum(II) Thiocyanate Species

Phosphorescent Cyclometalated Palladium(II) and Platinum(II) Complexes Derived from Diaminocarbene Precursors

Four‐Membered Bimetallic Carbon Complex [(M(η5‐C5(CH3)5))2(μ‐NPh)(μ‐C)] (M=Fe, Ru, Os) – An Ambiphilic Carbene with Lone Pair and σ‐Hole Reactivity

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Four‐Membered Bimetallic Carbon Complex [(M(η⁵‐C₅(CH₃)₅))₂(μ‐NPh)(μ‐C)] (M=Fe, Ru, Os) – An Ambiphilic Carbene with Lone Pair and σ‐Hole Reactivity