We systematically investigated iodine–metal and iodine–iodine bonding in van Koten’s pincer complex and 19 modifications changing substituents and/or the transition metal with a PBE0–D3(BJ)/aug–cc–pVTZ/PP(M,I) model chemistry. As a novel tool for the quantitative assessment of the iodine–metal and iodine–iodine bond strength in these complexes we used the local mode analysis, originally introduced by Konkoli and Cremer, complemented with NBO and Bader’s QTAIM analyses. Our study reveals the major electronic effects in the catalytic activity of the M–I–I non-classical three-center bond of the pincer complex, which is involved in the oxidative addition of molecular iodine I2 to the metal center. According to our investigations the charge transfer from the metal to the σ* antibonding orbital of the I–I bond changes the 3c–4e character of the M–I–I three-center bond, which leads to weakening of the iodine I–I bond and strengthening of the metal–iodine M–I bond, facilitating in this way the oxidative addition of I2 to the metal. The charge transfer can be systematically modified by substitution at different places of the pincer complex and by different transition metals, changing the strength of both the M–I and the I2 bonds. We also modeled for the original pincer complex how solvents with different polarity influence the 3c–4e character of the M–I–I bond. Our results provide new guidelines for the design of pincer complexes with specific iodine–metal bond strengths and introduce the local vibrational mode analysis as an efficient tool to assess the bond strength in complexes.
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Orbital analysis of bonding in diarylhalonium salts and relevance to periodic trends in structure and reactivity
Diarylhalonium compounds provide new opportunities as reagents and catalysts in the field of organic synthesis. The three center, four electron (3c–4e) bond is a center piece of their reactivity, but structural variation among the diarylhaloniums, and in comparison with other λ 3 -iodanes, indicates that the model needs refinement for broader applicability. We use a combination of Density Functional Theory (DFT), Natural Bond Orbital (NBO) Theory, and X-ray structure data to correlate bonding and structure for a λ 3 -iodane and a series of diarylchloronium, bromonium, and iodonium salts, and their isoelectronic diarylchalcogen counterparts. This analysis reveals that the s-orbital on the central halogen atom plays a greater role in the 3c–4e bond than previously considered. Finally, we show that our revised bonding model and associated structures account for both kinetic and thermodynamic reactivity for both acyclic phenyl(mesityl)halonium and cyclic dibenzohalolium salts.
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- Award ID(s):
- 1856705
- NSF-PAR ID:
- 10343348
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 13
- Issue:
- 22
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 6532 to 6540
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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We provide a didactic introduction to 2nd‐quantized representation of complex electron–hole (
e /h ) excitation patterns in general configuration interaction wave functions built from orthonormal local orbitals of natural atomic orbital or natural bond orbital (NBO) type. Such local excitation patterns of chemically oriented basis functions can be related to the resonance concepts of valence bond theory, and quantitative evaluation of the associated excitation probabilities then provides an alternative assessment of resonance “weighting” that may be compared with those of NBO‐based natural resonance theory. We illustrate the usefulness of anticommutation relations in deriving Pauli‐compliant expressions for allowed excitation patterns, showing how the exciton‐like promotions φλ → φν(creating ane /h excitation withh in φλande in φν) impose strict constraints on associatede /h ‐probabilities (requiring, e.g., that thee ‐probability for an electron “to be” or “not to be” in φνmust be rigorously linked to the complementaryh ‐probabilities in φλ). Specific examples are presented of the quantum Boolean logic for four or six local spin‐orbitals, with emphasis on Natural Poly‐Electron Population Analysis (NPEPA) evaluation of VB‐type covalent and ionic contributions in conventional 2‐center bonding, resonance weightings in 3‐center hydrogen bonding, and general characteristics of higher‐orderm ‐center bonding motifs form > 3. Numerical results are presented for methylamine, acrolein, and water dimer to illustrate current NPEPA implementation in the NBO program. © 2019 Wiley Periodicals, Inc. -
The relationship between solid-state supramolecular interactions and crystal habits is highlighted based on experimental and computational analysis of the crystal structure of strong halogen-bonded (HaB) associations between iodine-containing dihalogens (ICl, IBr) with 1,4-diazabicyclo[2,2,2]octane (DABCO) as well as with substituted pyridines and phenazine. The pattern of the energy frameworks and the interplay of the attractive and repulsive interactions in the solid-state associations involving these HaB donors and acceptors directly correlated with their crystal habits. This correlation suggests that analysis of the energy framework serves as a useful tool (complementary to the earlier developed methods) to rationalize and predict the crystal habit. The X-ray structural analysis also revealed that the I⋯N distances in the complexes were in the 2.24–2.54 Å range, i.e. they were much closer to the I⋯N covalent bond length than to the van der Waals separation. The computational analysis of the nature of halogen bonding in these complexes showed delocalization of their molecular orbitals' between donor and acceptors resulting in a substantial charge transfer from the nucleophiles to dihalogens and elongation of the I⋯X bond. As a result, both I⋯N and I⋯X bonds in the strongest complexes ( e.g. , ICl with DABCO or 4-dimethylaminopyridine) are characterized by the comparable Mayer bonds orders of about 0.6, along with the electron and energy densities at their bond critical points of about 0.1 a.u. and −0.02 a.u., respectively. These data as well as the density overlap regions indicator (DORI) point to the covalency of the I⋯N bonding and suggest that the interaction within the IX complexes can be described as (unsymmetrical) hypervalent 3c/4e N⋯I⋯X bonding akin to that in trihalide or halonium ions.more » « less
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Abstract The 1 : 2 reaction of the imidazole‐based dithiolate (
2 ) with GeCl2 • dioxane in THF/TMEDA gives3 , a TMEDA‐complexed dithiolene‐based germylene. Compound3 is converted to monothiolate‐complexed (5 ) and N‐heterocyclic carbene‐complexed (7 ) germanium(II) dithiolene complexes via Lewis base ligand exchange. A bis‐dithiolene‐based germylene (8 ), involving a 3c–4e S‐Ge‐S bond, has also been synthesized through controlled hydrolysis of7 . The bonding nature of3 ,5 , and8 was investigated by both experimental and theoretical methods. -
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Abstract A unique thorium‐thorium bond was observed in the crystalline tri‐thorium cluster [{Th(η8‐C8H8)(μ3‐Cl)2}3{K(THF)2}2]∞, though the claim of σ‐aromaticity for Th3bond has been questioned. Herein, a new type of core–shell syngenetic bonding model is proposed to describe the stability of this tri‐thorium cluster. The model involves a 3c–2e bond in the Th3core and a multicentered (ThCl2)3charge‐shift bond with 12 electrons scattering along the outer shell. To differentiate the strengths of the 3c–2e bond and the charge‐shift bond, the block‐localized wavefunction (BLW) method which falls into the ab initio valence bond (VB) theory is employed to construct a strictly core/shell localized state and its contributing covalent resonance structure for the Th3core bond. By comparing with the σ‐aromatic H3+and nonaromatic Li3+, the computed resonance energies and extra cyclic resonance energies confirm that this Th3core bond is truly delocalized and σ‐aromatic.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d2sc02332f
