On the nature of the short Pt–Tl bonds in model compounds [H5Pt–TlHn]n−

Pyykkö, Pekka; Patzschke, Michael

doi:10.1039/b211364c

Cited by 16 publications

(17 citation statements)

References 46 publications

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“…Previous experimental and theoretical studies have concluded that for the series I-V the oxidation states lie somewhere between Pt IV and Pt II and between Tl I and Tl III . 19,24,25 If we inspect the Hirshfeld charges in the various computational models (Table 3), obviously there is no resemblance to the oxidation states reported previously, but also not to their trends. For instance, for Tl the trend of increasing oxidation number deduced experimentally 19 is not visible in the calculated positive charges along the series.…”

Section: Pt and Tl Oxidation Statesmentioning

confidence: 88%

NMR properties of platinumthallium bonded complexes: analysis of relativistic density functional theory results

2004

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The metal NMR parameters of the complexes [(NC)(5)Pt-Tl(CN)(n)](n -) (n = 0-3, I-IV) and [(NC)(5)Pt-Tl-Pt(CN)(5)](3-) (V), as well as [{Pt(NO(3))(NH(3))(2)L(2)}Tl(NO(3))(2)(MeOH)] (VI) and [{Pt(NO(3))(NH(3))(2)L(2)}(2)Tl](+) (VII) with L = NHCO(t)Bu, were computationally investigated by relativistic density functional theory. Complexes I-V were previously studied by us. We briefly review the main findings here. Their spin-spin coupling constants are analyzed in terms of molecular orbital and fragment orbital contributions which demonstrate the various influences of the solvent and of the ligands on the extraordinarily large metal-metal coupling constants. Complexes VI and VII and various model systems were investigated in more detail. It is shown that the same computational model which performs best for I-V yields too large metal-metal coupling constants for VI and VII. The analysis shows that this is likely to be attributable to a strong sensitivity of the coupling constants to the rather small Pt 6s contributions in the occupied metal-metal sigma-bonding orbitals. Bulk solvent effects on the metal-metal couplings are sizeable and should be considered in the computational model. Both calculated and experimental Pt--Tl coupling constants for VI and VII are substantially larger than those for I-V, thereby representing the largest heteronuclear coupling constants known so far experimentally. Metal chemical shifts for VI and VII were also investigated. The computational results indicate that the choice of the Pt reference is rather problematic. Tl chemical shifts agree much better with experimental data.

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Section: Pt and Tl Oxidation Statesmentioning

confidence: 88%

NMR properties of platinumthallium bonded complexes: analysis of relativistic density functional theory results

2004

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“…This and related systems have also been theoretically studied in Refs. [57,58]. In the latter work (model systems with CN -replaced by H -), the unusually short Pt-Tl distance of approx.…”

Section: Two-component Zora-dft Calculationsmentioning

confidence: 91%

Relativistic Calculations of Spin–Spin Coupling Constants of Heavy Nuclei

Autschbach

Ziegler

2004

Calculation of NMR and EPR Parameters

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“…The M-M' systems herein are akin to other systems shown in the literature with varying degrees of metal-metal distances and deviations in geometryone in particular showing rather strong Pt(II)-Tl(III) polar-covalent bonding in [(NC) 5 Pt-Tl(CN) n ] n -complexes discovered by Glaser and co-workers that possess short intramolecular M-M' distances; subsequent computational studies completed by Pyykkö and Patzschke supported the polar-covalent bond argument. [79,80] In Glaser's complexes, the Pt(II)-Tl(III) centers exhibit a difference in electronegativity with corresponding orbital energy mismatch, leading to a significant shortening of M-M' distances. For the closed-shell metal center complexes herein, on the other hand, d 10 All That Glitters Is Not Gold of the lighter metal center to the Au(I) organometallic center, leading to short intramolecular M-M' distances.…”

Section: Photophysical Propertiesmentioning

confidence: 99%

All That Glitters Is Not Gold: A Computational Study of Covalent vs Metallophilic Bonding in Bimetallic Complexes of d¹⁰ Metal Centers—A Tribute to Al Cotton on the Tenth Anniversary of His Passing

Otten

Melancon

Omary

2018

Comments on Inorganic Chemistry

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As the tenth year that follows the premature passing of the inorganic chemistry legend F. Albert (Al) Cotton comes to a close, we provide some soul food that we believe Al would have enjoyed as he looks down upon two generations of disciples, a grandchild and two great grandchildren, in his scientific family tree. This article also represents a new tradition by which the editors of Comments on Inorganic Chemistry wish to lead by example, whereby we start publishing original research content that nonetheless preserves the journal's identity as a niche for "critical discussion of the current literature" of inorganic chemistry. Thus, we show novel demonstrations of a posteriori validation and a priori prediction of possible counterintuitive covalent M-M' bonds-after and before synthesis, respectively-contrasted with non-covalent M•••M interactions of the metallophilic type in bridge-dimeric systems of d 10 metal centers. Mixing of (n + 1

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On the nature of the short Pt–Tl bonds in model compounds [H₅Pt–TlH_n]ⁿ⁻

Abstract: RHF, DFT and MP2 calculations are reported for the compounds [H5Pt-TlHn]n-, n = 0-2. These serve as analogues for the experimentally known [(NC)5Pt-Tl(CN)n](n-)-species. The very short bond between platinum and thallium is discussed.

Cited by 16 publications

References 46 publications

NMR properties of platinumthallium bonded complexes: analysis of relativistic density functional theory results

NMR properties of platinumthallium bonded complexes: analysis of relativistic density functional theory results

Relativistic Calculations of Spin–Spin Coupling Constants of Heavy Nuclei

All That Glitters Is Not Gold: A Computational Study of Covalent vs Metallophilic Bonding in Bimetallic Complexes of d¹⁰ Metal Centers—A Tribute to Al Cotton on the Tenth Anniversary of His Passing

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On the nature of the short Pt–Tl bonds in model compounds [H5Pt–TlHn]n−

Abstract: RHF, DFT and MP2 calculations are reported for the compounds [H5Pt-TlHn]n-, n = 0-2. These serve as analogues for the experimentally known [(NC)5Pt-Tl(CN)n](n-)-species. The very short bond between platinum and thallium is discussed.

Cited by 16 publications

References 46 publications

NMR properties of platinumthallium bonded complexes: analysis of relativistic density functional theory results

NMR properties of platinumthallium bonded complexes: analysis of relativistic density functional theory results

Relativistic Calculations of Spin–Spin Coupling Constants of Heavy Nuclei

All That Glitters Is Not Gold: A Computational Study of Covalent vs Metallophilic Bonding in Bimetallic Complexes of d10 Metal Centers—A Tribute to Al Cotton on the Tenth Anniversary of His Passing

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On the nature of the short Pt–Tl bonds in model compounds [H₅Pt–TlH_n]ⁿ⁻

All That Glitters Is Not Gold: A Computational Study of Covalent vs Metallophilic Bonding in Bimetallic Complexes of d¹⁰ Metal Centers—A Tribute to Al Cotton on the Tenth Anniversary of His Passing