Probing relativistic effects in the gas-phase CS2 ligation of late transition metal cations (groups 9–11) with rate measurements and quantum chemical calculations of ligation energies

Blagojevic, Voislav; Koyanagi, Gregory K.; Kiani, Pirouz; Pietro, William J.; Böhme, Diethard K.

doi:10.1016/j.ijms.2021.116525

Cited by 4 publications

(15 citation statements)

References 22 publications

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“…Overview of the trend in t he relativistic contribution to the M + –CS 2 bond energy going down the periodic table (Blagojevic et al, 2021)…”

Section: Trends In Ligation Kineticsmentioning

confidence: 99%

“…F I G U R E 13 Measured trends down the periodic table in the effective bimolecular rate coefficient for the ligation of d 10 s 1 atomic transition metal cations with five different ligands at 295 ± 2 K in He at 0.35 ± 0.01 Torr (Blagojevic et al, 2018) F I G U R E 14 Measured trends across the periodic table in the effective bimolecular rate coefficient for the ligation of third-row atomic transition metal cations with six different ligands at 295 ± 2 K in He at 0.35 ± 0.01 Torr (Blagojevic et al, 2018) F I G U R E 15 Variation in the ligation efficiency, k/k c , of CS 2 adding to bare atomic transition metal cations, M + , down the periodic table for Row 1-3 atomic cations in Group 9-11 at room temperature (Blagojevic et al, 2021) F I G U R E 16 Variation in the ligation efficiency, k/k c , of CS 2 adding to ligated atomic transition metal cations, M + (CS 2 ), down the periodic table for Row 1-3 atomic cations in Group 9-11, at room temperature (Blagojevic et al, 2021) ICP-SIFT MS, a derivative of FA and SIFT MS, has proven to be an extraordinarily powerful technique for the exploration of the intrinsic kinetics and chemistry of atomic ion-molecule reactions in general and atomic ion ligation in particular. My journey leading to its invention and subsequent application has been most rewarding.…”

Section: Group 12 (D 10 S 1 ) Metal Cationsmentioning

confidence: 99%

“…Our latest ligand of interest was CS 2 , in part because the results of our measurements allowed an assessment of relativistic effects in the addition of both the first and the second ligand to an atomic cation (Blagojevic et al, 2021). The strong relativistic effects that were observed are shown in Figure 15.…”

Section: Trends In Ligation Kineticsmentioning

confidence: 99%

“…Variation in the ligation efficiency, k / k c , of CS 2 adding to ligated atomic transition metal cations, M + (CS 2 ), down the periodic table for Row 1–3 atomic cations in Group 9–11, at room temperature (Blagojevic et al, 2021)…”

Section: Trends In Ligation Kineticsmentioning

confidence: 99%

“…DFT/DKH2/B2PW91/jorge‐TZP‐DKH/D3 calculated M + –CS 2 bond dissociation energies (kJ mol −1 ) for M + (CS 2 ) 2 at 298 K (Blagojevic et al, 2021). DFT, density functional theory…”

Section: Trends In Ligation Kineticsmentioning

confidence: 99%

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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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“…Overview of the trend in t he relativistic contribution to the M + –CS 2 bond energy going down the periodic table (Blagojevic et al, 2021)…”

Section: Trends In Ligation Kineticsmentioning

confidence: 99%

Section: Group 12 (D 10 S 1 ) Metal Cationsmentioning

confidence: 99%

Section: Trends In Ligation Kineticsmentioning

confidence: 99%

Section: Trends In Ligation Kineticsmentioning

confidence: 99%

“…DFT/DKH2/B2PW91/jorge‐TZP‐DKH/D3 calculated M + –CS 2 bond dissociation energies (kJ mol −1 ) for M + (CS 2 ) 2 at 298 K (Blagojevic et al, 2021). DFT, density functional theory…”

Section: Trends In Ligation Kineticsmentioning

confidence: 99%

See 3 more Smart Citations