Bond dissociation energies of FeB, CoB, NiB, RuB, RhB, OsB, IrB, and PtB

Merriles, Dakota M.; Tieu, Erick; Morse, Michael D.

doi:10.1063/1.5113511

Cited by 33 publications

(53 citation statements)

References 72 publications

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“…The first entry in Table for each species describes dissociation to the two products in their ground electronic states. Our computed value of 508 kJ/mol for RhB is in excellent agreement with a recent experimental measurement of 506.7 kJ/mol . The second entry for each species in Table describe dissociation to the products in their states that are ready to form the respective multiple bonds, i.e., Rh in its 4d 9 ( 2 D) configuration for Rh≣B and BH in its σ sp 1 π 1 ( 3 Π) configuration for RhBH + .…”

supporting

confidence: 87%

“…Our computed value of 508 kJ/mol for RhB is in excellent agreement with a recent experimental measurement of 506.7 kJ/mol. 30 The second entry for each species in Table 1 describe dissociation to the products in their states that are ready to form the respective multiple bonds, i.e., Rh in its 4d 9 ( 2 D) configuration for Rh≣B and BH in its σ sp 1 π 1 ( 3 Π) configuration for RhBH + . The latter should be more relevant to the intrinsic bond strength.…”

mentioning

confidence: 99%

“…The extremely short Rh–B bond length is consistent with a quadruple bond between Rh and B (Rh≣B). The RhB bonding was considered to be a triple bond previously because the 1σ MO was classified essentially as a 2s lone pair. ,, However, the bonding nature of the 1σ MO can be glimpsed by the fact that the bent Rh≣B(BO – ) structure is more stable than the linear RhB–BO – isomer, in which the B atom can form only a triple bond with Rh. The bonding of the two structures is compared in Figure S5 using the Adaptive Natural Density Partitioning (AdNDP) analyses .…”

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confidence: 99%

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Observation of Four-Fold Boron–Metal Bonds in RhB(BO^–) and RhB

Cheung

Chen

Kocheril

et al. 2020

J. Phys. Chem. Lett.

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The maximum bond order between two main-group atoms was known to be three. However, it has been suggested recently that there is quadruple bonding in C 2 and analogous eight-valence electron species. While the quadruple bond in C 2 has aroused some debates, an interesting question is: are main-group elements capable of forming quadruple bonds? Here we use photoelectron spectroscopy and computational chemistry to probe the electronic structure and chemical bonding in RhB 2 O − and RhB − and show that the boron atom engages in quadruple bonding with rhodium in RhB(BO) − and neutral RhB. The quadruple bonds consist of two πbonds formed between the Rh 4d xz /4d yz and B 2p x /2p y orbitals and two σ-bonds between the Rh 4d z 2 and B 2s/2p z orbitals. To confirm the quadruple bond in RhB, we also investigate the linear RhB−H + species and find a triple bond between Rh and B, which has a longer bond length, lower stretching frequency, and smaller bond dissociation energy in comparison with that of the Rh≣B quadruple bond in RhB.

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confidence: 87%

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confidence: 99%

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confidence: 99%

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Observation of Four-Fold Boron–Metal Bonds in RhB(BO^–) and RhB

Cheung

Chen

Kocheril

et al. 2020

J. Phys. Chem. Lett.

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“…Also listed are respective values obtained in previous studies. 6,10,11 The experimental equilibrium distance is 1.692 Å. 6 The experimental ground state dissociation energy recently obtained using the predissociation threshold approach is 120.8 kcal mol −1 , slightly higher than the previous measurement of 112.7 kcal mol −1 obtained via Knudsen effusion mass spectroscopy.…”

Section: Wave Functions and Energies Of The Sixmentioning

confidence: 73%

“…6,10,11 The experimental equilibrium distance is 1.692 Å. 6 The experimental ground state dissociation energy recently obtained using the predissociation threshold approach is 120.8 kcal mol −1 , slightly higher than the previous measurement of 112.7 kcal mol −1 obtained via Knudsen effusion mass spectroscopy. 5 Thus, the ground state equilibrium distance of 1.701 Å and the binding energy of −119.1 kcal mol −1 , computed in the present work, are in gratifying agreement with experiment.…”

Section: Wave Functions and Energies Of The Sixmentioning

confidence: 73%

Multiple Bonding in Rhodium Monoboride. Quasi-atomic Analyses of the Ground and Low-Lying Excited States

2021

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The bonding structures of the ground state and the lowest five excited states of rhodium monoboride are identified by determining the quasi-atomic orbitals in full valence space MCSCF wave functions and the interactions between these orbitals. A quadruple bond, namely two π-bonds and two σ-bonds, is identified and characterized for the X1Σ+ ground state, in agreement with a previous report ( Cheung Cheung J. Phys. Chem. Lett202011659663). However, in all excited states, the bonding is predicted to be weaker because, in these states, one of the σ-bonding interactions has a small magnitude. In the a3Δ and A1Δ states, the bond order is between a triple and quadruple bond. In the b3Σ+ state, the Rh–B linkage is a triple bond. In the c3Π and B1Π states, the atoms are linked by a double bond due to an additional weakening of the two π-bonds. The decreases in the predicted bond strengths are reflected in the decreases of the predicted binding energies and in the increases of the predicted bond lengths from the X1Σ+ ground state to the c3Π and the B1Π excited states. Notably, the 5pσ orbital of rhodium, which is vacant in the ground state of the atom, plays a significant role in the molecule.

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Quest of Quadruple Bonding Between Two Main‐Group Atoms in AeB⁻ and AeC (Ae=Ca, Sr, Ba) and the Role of d Orbitals of Heavier Alkaline‐Earth Atoms in Covalent Interactions

Liu

Wang

Yan

et al. 2023

Chemistry A European J

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Quantum chemical calculations using ab initio methods at the MRCI+Q(6,8)/def2‐QZVPP and CCSD(T)/def2‐QZVPP levels as well as density functional theory are reported for the diatomic molecules AeB− and isoelectronic AeC (Ae=Ca, Sr, Ba). The boride anions AeB− have an electronic triplet (3Σ−) ground state. The quintet (5Σ−) state is 5.8–12.3 kcal/mol higher in energy and the singlet (1Δ) state is 13.1–15.3 kcal/mol above the triplet. The isoelectronic AeC molecules are also predicted to have a low‐lying triplet (3Σ−) state but the quintet (5Σ−) state is only 2.2 kcal/mol (SrC) and 2.9 kcal/mol (CaC) above the triplet state. The triplet (3Σ−) and quintet (5Σ−) states of BaC are nearly isoenergetic. All systems have rather strong bonds. The calculated bond dissociation energies of the triplet (3Σ−) state are between De=38.3–41.7 kcal/mol for AeB− and De=49.4–57.5 kcal/mol for AeC. The barium species have always the strongest bonds whereas the calcium and strontium compounds have similar BDEs. The bonding analysis indicates that there is little charge migration in AeB− in the direction Ae→B− where the alkaline earth atoms carry positive charges between 0.09 e–0.22 e. The positive charges at the Ae atoms are much larger in AeC where the charge migration Ae→C is between 0.90 e–0.91 e. A detailed analysis of the interatomic interactions with the EDA‐NOCV method shows that all diatomic species AeB− and AeC are built from dative interactions between Ae (1S, ns2) and B− or C (3P, 2 s22pπ12pπ′1). The eventually formed bonds in AeC are better described in terms of interactions between the ions Ae+ (2S, ns1)+C− (4S, 2 s22pπ12pπ′12pσ1). Inspection of the orbital interactions suggests that the alkaline earth atoms Ca, Sr, Ba use mainly their (n‐1)d AOs besides the (n)s AOs for the covalent bonds. This creates a second energetically low‐lying σ‐bonding MO in the molecules, which feature valence orbitals with the order ϕ1 (σ‐bonding)<ϕ2 (σ‐bonding)<ϕ3 (degenerate π‐bonding). All four occupied valence MOs of AeB− and AeC are bonding orbitals. Since the degenerate π orbitals ϕ3 are only singly occupied, the formal bond order is three.

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Bond dissociation energies of FeB, CoB, NiB, RuB, RhB, OsB, IrB, and PtB

Cited by 33 publications

References 72 publications

Observation of Four-Fold Boron–Metal Bonds in RhB(BO^–) and RhB

Observation of Four-Fold Boron–Metal Bonds in RhB(BO^–) and RhB

Multiple Bonding in Rhodium Monoboride. Quasi-atomic Analyses of the Ground and Low-Lying Excited States

Quest of Quadruple Bonding Between Two Main‐Group Atoms in AeB⁻ and AeC (Ae=Ca, Sr, Ba) and the Role of d Orbitals of Heavier Alkaline‐Earth Atoms in Covalent Interactions

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Bond dissociation energies of FeB, CoB, NiB, RuB, RhB, OsB, IrB, and PtB

Cited by 33 publications

References 72 publications

Observation of Four-Fold Boron–Metal Bonds in RhB(BO–) and RhB

Observation of Four-Fold Boron–Metal Bonds in RhB(BO–) and RhB

Multiple Bonding in Rhodium Monoboride. Quasi-atomic Analyses of the Ground and Low-Lying Excited States

Quest of Quadruple Bonding Between Two Main‐Group Atoms in AeB− and AeC (Ae=Ca, Sr, Ba) and the Role of d Orbitals of Heavier Alkaline‐Earth Atoms in Covalent Interactions

Contact Info

Product

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Observation of Four-Fold Boron–Metal Bonds in RhB(BO^–) and RhB

Observation of Four-Fold Boron–Metal Bonds in RhB(BO^–) and RhB

Quest of Quadruple Bonding Between Two Main‐Group Atoms in AeB⁻ and AeC (Ae=Ca, Sr, Ba) and the Role of d Orbitals of Heavier Alkaline‐Earth Atoms in Covalent Interactions