An Electrophilic, Intramolecularly Base-Stabilized Platinum–Antimony Complex

Smith, Jesse Eyre; Yang, Haifeng; Gabbaı̈, François P.

doi:10.1021/acs.organomet.1c00371

Cited by 12 publications

(7 citation statements)

References 39 publications

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“…The shortness of the Au–Bi bond in 8 is presumably due to the bonding of the pincer-like [Au I (2-Me-8-qy)] 2 – ligand in 8 to the highly Lewis acidic Bi(III) atom in the (Bi III Cl) 2+ fragment. On this basis, we assume that this is a Au → Bi donor bond similar to those previously reported by Gabbaï and Limberg. − …”

Section: Resultssupporting

confidence: 76%

Highly Adaptive Nature of Group 15 Tris(quinolyl) Ligands─Studies with Coinage Metals

et al. 2023

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The substitution of heavier, more metallic atoms into classical organic ligand frameworks provides an important strategy for tuning ligand properties, such as ligand bite and donor character, and is the basis for the emerging area of main-group supramolecular chemistry. In this paper, we explore two new ligands [E(2-Me-8-qy)3] [E = Sb (1), Bi (2); qy = quinolyl], allowing a fundamental comparison of their coordination behavior with classical tris(2-pyridyl) ligands of the type [E′(2-py)3] (E = a range of bridgehead atoms and groups, py = pyridyl). A range of new coordination modes to Cu+, Ag+, and Au+ is seen for 1 and 2, in the absence of steric constraints at the bridgehead and with their more remote N-donor atoms. A particular feature is the adaptive nature of these new ligands, with the ability to adjust coordination mode in response to the hard–soft character of coordinated metal ions, influenced also by the character of the bridgehead atom (Sb or Bi). These features can be seen in a comparison between [Cu2{Sb(2-Me-8-qy)3}2](PF6)2 (1·CuPF6) and [Cu{Bi(2-Me-8-qy)3}](PF6) (2·CuPF6), the first containing a dimeric cation in which 1 adopts an unprecedented intramolecular N,N,Sb-coordination mode while in the second, 2 adopts an unusual N,N,(π-)C coordination mode. In contrast, the previously reported analogous ligands [E(6-Me-2-py)3] (E = Sb, Bi; 2-py = 2-pyridyl) show a tris-chelating mode in their complexes with CuPF6, which is typical for the extensive tris(2-pyridyl) family with a range of metals. The greater polarity of the Bi–C bond in 2 results in ligand transfer reactions with Au(I). Although this reactivity is not in itself unusual, the characterization of several products by single-crystal X-ray diffraction provides snapshots of the ligand transfer reaction involved, with one of the products (the bimetallic complex [(BiCl){ClAu2(2-Me-8-qy)3}] (8)) containing a Au2Bi core in which the shortest Au → Bi donor–acceptor bond to date is observed.

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Section: Resultssupporting

confidence: 76%

Highly Adaptive Nature of Group 15 Tris(quinolyl) Ligands─Studies with Coinage Metals

et al. 2023

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“…In estimating the two aforementioned reference δ P data, these authors used corrections for the difference in BMS values between the aqueous sample and the reference material. In turn, in the work [84], the 19 F NMR chemical shifts were referenced against CFCl 3 using BF 3 •Et 2 O as an external secondary standard with δ F = −153.0 ppm.…”

Section: Methods For 1 H/ 13 C Chemical Shift Referencementioning

confidence: 99%

On the Use of Deuterated Organic Solvents without TMS to Report 1H/13C NMR Spectral Data of Organic Compounds: Current State of the Method, Its Pitfalls and Benefits, and Related Issues

Nazarski

2023

Molecules

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The quite popular, simple but imperfect method of referencing NMR spectra to residual 1H and 13C signals of TMS-free deuterated organic solvents (referred to as Method A) is critically discussed for six commonly used NMR solvents with respect to their δH and δC data that exist in the literature. Taking into account the most reliable data, it was possible to recommend ‘best’ δX values for such secondary internal standards. The position of these reference points on the δ scale strongly depends on the concentration and type of analyte under study and the solvent medium used. For some solvents, chemically induced shifts (CISs) of residual 1H lines were considered, also taking into account the formation of 1:1 molecular complexes (for CDCl3). Typical potential errors that can occur as a result of improper application of Method A are considered in detail. An overview of all found δX values adopted by users of this method revealed a discrepancy of up to 1.9 ppm in δC reported for CDCl3, most likely caused by the CIS mentioned above. The drawbacks of Method A are discussed in relation to the classical use of an internal standard (Method B), two ‘instrumental’ schemes in which Method A is often implicitly applied, that is, the default Method C using 2H lock frequencies and Method D based on Ξ values, recommended by the IUPAC but only occasionally used for 1H/13C spectra, and external referencing (Method E). Analysis of current needs and opportunities for NMR spectrometers led to the conclusion that, for the most accurate application of Method A, it is necessary to (a) use dilute solutions in a single NMR solvent and (b) to report δX data applied for the reference 1H/13C signals to the nearest 0.001/0.01 ppm to ensure the precise characterization of new synthesized or isolated organic systems, especially those with complex or unexpected structures. However, the use of TMS in Method B is strongly recommended in all such cases.

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“…14,17 Gabbaï showed that both stiboranes and stibonium cations with sufficiently pronounced Lewis acidity can interact with oxygen atoms to form heterocycles (Scheme 1). 18–20 Even with lower Lewis acidity of the antimony atom, the formation of such (four-membered) antimony- and chalcogen-containing heterocycles was demonstrated. 21…”

Section: Introductionmentioning

confidence: 99%

Oxidation-dependent Lewis acidity in chalcogen adducts of Sb/P frustrated Lewis pairs

Krieft,

Neumann,

Stammler

et al. 2024

Dalton Trans.

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An Electrophilic, Intramolecularly Base-Stabilized Platinum–Antimony Complex

Cited by 12 publications

References 39 publications

Highly Adaptive Nature of Group 15 Tris(quinolyl) Ligands─Studies with Coinage Metals

Highly Adaptive Nature of Group 15 Tris(quinolyl) Ligands─Studies with Coinage Metals

On the Use of Deuterated Organic Solvents without TMS to Report 1H/13C NMR Spectral Data of Organic Compounds: Current State of the Method, Its Pitfalls and Benefits, and Related Issues

Oxidation-dependent Lewis acidity in chalcogen adducts of Sb/P frustrated Lewis pairs

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