Ligation kinetics as a probe for relativistic effects in ion chemistry: Gas-phase ligation of Ni+, Pd+ and Pt+ at room temperature

Blagojevic, Voislav; Lavrov, Vitali V.; Koyanagi, Gregory K.; Böhme, Diethard K.

doi:10.1016/j.ijms.2016.08.011

Cited by 10 publications

(10 citation statements)

References 26 publications

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“…After the Group 11 d 10 cations, we Immediately turned our attention to Group 10 d 9 cations in which Pt + is in the third row. Again, we observed a third‐row enhancement in the rate of ligation very similar to that for Au + as seen in Figure 10 (Blagojevic et al, 2017b). Computations again predicted that the enhancement observed with Pt + in the d 9 period also can be attributed to the extra stabilization due to relativistic effects in the binding of NH 3 to Pt + compared to Pd + and Ni + .…”

Section: Trends In Ligation Kineticssupporting

confidence: 83%

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Toward ICP‐SIFT mass spectrometry and atomic cation ligation as a probe of relativistic effects—A personal journey

Böhme

2021

Mass Spectrometry Reviews

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The ICP-SIFT mass spectrometer at York University, a derivative of flowing afterglow (FA) and selected-ion flow tube (SIFT) mass spectrometers, has provided a powerful technique to measure the chemistry and kinetics of atomic cation-molecule reactions. Here, I focus on periodic trends in the kinetics of ligation reactions of atomic ions with small molecules. I examine trends in ammonia ligation kinetics across the first two rows of the atomic transition metal cations and their correlation with ligand bond enthalpies and ligand field stabilization energies. Also explored are trends down Groups 1 and 2 in the kinetics of noncovalent electrostatic ligand bonding and the tendency for s electron solvation of the atomic alkaline-earth cations with ammonia. Finally, I briefly review trends observed with 12 different ligands in the ligation rate down the periodic table with Group 9-12 transition atomic metal cations. These trends provide a compelling probe for the presence of relativistic effects that influence the strengths of the metal-ion ligand bonds that are formed. There is a clear third-row rate enhancement with Ir + , Pt + , Au + , and Hg + , the extent of which depends on the nature of the ligand. This large set of kinetic data provides an unprecedented broad perspective of relativistic effects in ligand bonding. With CS 2 as a ligand, the third-row relativistic effect is apparent in the formation of both the first and the second ligand bond with the Groups 10 and 11 atomic cations as predicted by our quantum chemical calculations of ligation energies.

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Section: Trends In Ligation Kineticssupporting

confidence: 83%

“…Measured trends in the effective bimolecular rate coefficient for the ligation of d 9 atomic cations with six different ligands at 295 ± 2 K in He at 0.35 ± 0.01 Torr (Blagojevic et al, 2017b)…”

Section: Trends In Ligation Kineticsmentioning

confidence: 99%

Toward ICP‐SIFT mass spectrometry and atomic cation ligation as a probe of relativistic effects—A personal journey

Böhme

2021

Mass Spectrometry Reviews

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“…The study of the simple reactions M(NH 3 ) n + +NH 3 , can allow to gain some insight into the role played by the ligands on the reactivity exhibited by these systems (interestingly, these ammine‐complexes resemble the charge and the nitrogen environment surrounding the molybdenum compound reported in reference 4). These interactions have been investigated experimentally and theoretically by several authors [12–32] . Recently, Blagojevic et al.…”

Section: Introductionmentioning

confidence: 99%

Low‐Energy Pathways Found for the NH₃ Activation and H₂ Elimination by the Werner‐Type Complexes M(NH₃)₄⁺ (M=Fe, Ru and Os).

2020

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The interactions of NH3 with the transition metal complexes M(NH3)n+ (M=Fe, Ru, Os; n=0−4) were investigated theoretically with the aim of analyzing the factors that determine their reactivity patterns and product distributions. The reactions of ammonia with the low‐coordination complexes of the three metallic ions (n=1−3) lead only to the addition product M(NH3)n+1+. However, once the highest‐coordinated complex M(NH3)4+ is reached, each of the reactions evolves to metal‐inserted species through low energy channels. For osmium, the hydrogen abstraction from an additional NH3 molecule by the inserted intermediate H−Os(NH3)4‐NH2+ leads to H2 elimination products along a favorable pathway. The facile breaking of the strong N−H bond of ammonia by these Werner‐type complexes is by far the most striking finding emerging from this study. Hopefully, this could inspire future contributions in the areas of chemical and bioinorganic catalysis.

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“…Bimolecular H 2 elimination reactions were observed for early atomic transition metal cations: Sc þ and Ti þ in the first row; Y þ , Zr þ , and Nb þ in the second row; and La þ , Hf þ , Ta þ , W þ , Re þ , Os þ , and Ir þ in the third row, and these will be presented separately. 13 Of the remaining thirdrow cations, Pt þ and Au þ reacted by ligation that is dominated by relativistic effects, 5,6 and Hg þ reacts with ammonia by electron transfer. 14 As an indication of the quality of our experimental measurements, we provide our experimental results for the ammonia ligation of the first-row cations Cr þ , Fe þ , Co þ , and Zn þ (see Figure 1) and the second-row cations Mo þ , Ru þ , Rh þ , and Cd þ (see Figure 2).…”

Section: Resultsmentioning

confidence: 99%

“…Third row transition metal cations were observed to react mainly in a bimolecular fashion; only Pt þ and Au þ undergo ammonia addition and the rates for these ligation reactions we have shown previously to be dominated by relativistic effects. [5][6][7] Ammonia is regarded as a moderate-field ligand, in terms of the degree of d-orbital splitting due to the ligation of atomic metal cations; ligand field effects of ammonia lie in the middle between low (e.g. I À ) and high (e.g.…”

Section: Introductionmentioning

confidence: 99%

Ligation kinetics as a probe for gas-phase ligand field effects: Ligation of atomic transition metal cations with ammonia at room temperature

Blagojevic

Lavrov

Koyanagi

et al. 2019

Eur J Mass Spectrom (Chichester)

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The kinetics of ammonia ligation to atomic first and second row transition metal cations were measured in an attempt to assess the role of ligand field effects in gas-phase ion-molecule reaction kinetics. Measurements were performed at 295 AE 2 K in helium bath gas at 0.35 Torr using an inductively coupled plasma/selected-ion flow tube tandem mass spectrometer. The atomic cations were produced at ca. 5500 K in an inductively coupled plasma source and were allowed to decay radiatively and to thermalize by collisions with argon and helium atoms prior to reaction. A strong correlation was observed across the periodic table between the measured rate coefficients for ammonia ligation and measured/calculated bond dissociation energies. A similar strong correlation is seen with the ligand field stabilization energy. So ligand field stabilization energies should provide a useful predictor of relative rates of ligation of atomic metal ions.

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Ligation kinetics as a probe for relativistic effects in ion chemistry: Gas-phase ligation of Ni+, Pd+ and Pt+ at room temperature

Cited by 10 publications

References 26 publications

Toward ICP‐SIFT mass spectrometry and atomic cation ligation as a probe of relativistic effects—A personal journey

Toward ICP‐SIFT mass spectrometry and atomic cation ligation as a probe of relativistic effects—A personal journey

Low‐Energy Pathways Found for the NH₃ Activation and H₂ Elimination by the Werner‐Type Complexes M(NH₃)₄⁺ (M=Fe, Ru and Os).

Ligation kinetics as a probe for gas-phase ligand field effects: Ligation of atomic transition metal cations with ammonia at room temperature

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Ligation kinetics as a probe for relativistic effects in ion chemistry: Gas-phase ligation of Ni+, Pd+ and Pt+ at room temperature

Cited by 10 publications

References 26 publications

Toward ICP‐SIFT mass spectrometry and atomic cation ligation as a probe of relativistic effects—A personal journey

Toward ICP‐SIFT mass spectrometry and atomic cation ligation as a probe of relativistic effects—A personal journey

Low‐Energy Pathways Found for the NH3 Activation and H2 Elimination by the Werner‐Type Complexes M(NH3)4+ (M=Fe, Ru and Os).

Ligation kinetics as a probe for gas-phase ligand field effects: Ligation of atomic transition metal cations with ammonia at room temperature

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Low‐Energy Pathways Found for the NH₃ Activation and H₂ Elimination by the Werner‐Type Complexes M(NH₃)₄⁺ (M=Fe, Ru and Os).