Tin(IV) Compounds with 2-C6F4PPh2 Substituents and Their Reactivity toward Palladium(0): Formation of Tin–Palladium Complexes via Oxidative Addition

Wächtler, Eberhard; Wahlicht, Sven; Privér, Steven H.; Bennett, Martin A.; Gerke, Birgit; Pöttgen, Rainer; Brendler, Erica; Gericke, Robert; Wagler, Jörg; Bhargava, Suresh K.

doi:10.1021/acs.inorgchem.7b00410

Cited by 13 publications

(3 citation statements)

References 61 publications

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“…Although the subsequent HCl elimination was significantly endergonic (Δ G ° = 16.5 kcal/mol), it is likely that PPh 3 acts as an acceptor and/or scavenger of HCl to make the reaction feasible in a way similar to that proposed for the Sn–F bond cleavage . DFT computational results of Sn–Cl bond activation are basically consistent with the early study on Sn–Cl bond activation by Pt complexes, in which S N 2-type pathway was proposed . The mechanistic difference between Sn–F and Sn–Cl bond activation would be attributed to the bonding natures of the Ir → Sn–X interactions, and the simultaneous formation of strong H–F bond appears to be required for the cleavage of stronger Sn–F bond than Sn–Cl bond.…”

Section: Resultssupporting

confidence: 86%

Iridium Hydride Mediated Stannane–Fluorine and −Chlorine σ-Bond Activation: Reversible Switching between X-Type Stannyl and Z-Type Stannane Ligands

et al. 2017

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Iridium(I) carbonyl hydride Ir(H)(CO)(PPh3)3 (1) cleaves the Sn–F and Sn–Cl bonds of four-coordinate stannanes {o-(Ph2P)C6H4}3Sn(X) (X = F (2a) and Cl(2b)) to afford the stannyl complex [{o-(Ph2P)C6H4}3Sn]Ir(CO) (3) and HX (X = F and Cl) thanks to phosphine chelation. A plausible intermediate [{o-(Ph2P)C6H4}3(Cl)Sn]Ir(H)(CO) (6) featuring Z-type Ir → R3SnCl interaction was synthesized by the reaction of 3 with HCl. Compound 6 readily regenerated 3 upon treatment with Brønsted bases, enabling reversible switching between X-type stannyl and Z-type stannane ligands. Density functional theory calculations suggest plausible pathways for Sn–F and Sn–Cl bond cleavage reactions and support the idea that the species bearing a Z-type Ir → R3SnX interactions (X = F and Cl) are intermediates for Sn–X bond cleavage.

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Section: Resultssupporting

confidence: 86%

Iridium Hydride Mediated Stannane–Fluorine and −Chlorine σ-Bond Activation: Reversible Switching between X-Type Stannyl and Z-Type Stannane Ligands

et al. 2017

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“…Scheme 5 shows that stannanes of type J can lead to PSnP stannyl palladium(II)complexes via oxidative addition of Sn−C or Sn−Cl bonds [73] . The oxidative addition of the Sn−C Me bond of J was not observed.…”

Section: Synthetic Approachesmentioning

confidence: 99%

Tetrelanes versus Tetrylenes as Precursors to Transition Metal Complexes Featuring Tridentate PEP Tetryl Ligands (E=Si, Ge, Sn)

Cabeza

García‐Álvarez

2023

Chemistry A European J

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Two synthetic approaches have until now been used to synthesize transition metal complexes having a tridentate (pincer or tripod) PEP tetryl (E=Si, Ge, Sn) ligand. These approaches differ in the metal-free precursor, tetrelane or tetrylene, that gives rise to the corresponding PEP tetryl ligand. Tetrelanes (PSiP silanes, PGeP germanes and PSnP stannanes and simple phosphane-free stannanes) have led to tetryl ligands by oxidatively adding an EÀ X bond (X=H, C or halogen in most cases) to the metal atom of a low-valent transition metal complex, whereas tetrylenes (PGeP germylenes and PSnP stannylenes) have led to tetryl ligands upon insertion of their E atom into an MÀ X bond (X=Cl in most cases) of the metal precursor or through a derivatization of the E atom after the tetrylene fragment is coordinated to the metal. For each synthetic approach, all the currently known types of PEP tetryl ligand frameworks that have been found in transition metal complexes are presented and discussed in this review.

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“…PSiP, PSiN, and NSiN pincer complexes have been studied for Si–H bond activation, C–H borylation of arenes, hydrocarboxylation of allenes, dehydrogenative borylation, fluorosilane activation, and hydroborylation of CO 2 . − A PGeP pincer complex of Pd has been studied as a catalyst for the hydrocarboxylation of allenes and the hydrometallation of ethylene . The heterobimetallic bonding interaction between the group 14 element (E = Ge or Sn, sometimes referred to as “tetrel”) and Ni, Pd, or Pt in SES and PEP complexes has been studied (E = group 14 element). − PEP (E = Si, Ge, and Sn) complexes of Pd were demonstrated to be active catalysts for a reductive aldol-type reaction . PSnP complexes of group 10 metals undergo Sn–Cl bond activation and alkyl transfer .…”

Section: Introductionmentioning

confidence: 99%

Phosphine Ligand Binding and Catalytic Activity of Group 10–14 Heterobimetallic Complexes

Daniels

Atterberry

et al. 2022

Inorg. Chem.

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Heterobimetallic complexes have attracted much interest due to their broad range of structures and reactivities as well as unique catalytic abilities. Additionally, these complexes can be utilized as single-source precursors for the synthesis of binary intermetallic compounds. An example is the family of bis(pyridine-2-thiolato)dichloro-germanium and tin complexes of group 10 metals (Pd and Pt). The reactivity of these heterobimetallic complexes is highly tunable through substitution of the group 14 element and the neutral ligand bound to the transition metal. Here, we study the binding energies of three different phosphorous-based ligands, PR3 (R = Bu, Ph, and OPh) by density functional theory and restricted Hartree–Fock methods. The PR3 ligand-binding energies follow the trend of PBu3 > PPh3 > P(OPh)3, in agreement with their sigma-bonding ability. These results are confirmed by ligand exchange experiments monitored with 31P NMR spectroscopy, in which a weaker binding PR3 ligand is replaced with a stronger one. Furthermore, we demonstrate that the heterobimetallic complexes are active catalysts in the Negishi coupling reaction, where stronger binding PR3 ligands inhibit access to an active site at the metal center. Similar strategies could be applied to other complexes to better understand their ligand-binding energetics and predict their reactivity as both precursors and catalysts.

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Tin(IV) Compounds with 2-C₆F₄PPh₂ Substituents and Their Reactivity toward Palladium(0): Formation of Tin–Palladium Complexes via Oxidative Addition

Cited by 13 publications

References 61 publications

Iridium Hydride Mediated Stannane–Fluorine and −Chlorine σ-Bond Activation: Reversible Switching between X-Type Stannyl and Z-Type Stannane Ligands

Iridium Hydride Mediated Stannane–Fluorine and −Chlorine σ-Bond Activation: Reversible Switching between X-Type Stannyl and Z-Type Stannane Ligands

Tetrelanes versus Tetrylenes as Precursors to Transition Metal Complexes Featuring Tridentate PEP Tetryl Ligands (E=Si, Ge, Sn)

Phosphine Ligand Binding and Catalytic Activity of Group 10–14 Heterobimetallic Complexes

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