The first examples of triply bonded dirhenium(II,II) complexes that contain bis(diphenylphosphino)methane and dithiocarbamato ligands: spectroscopic, structural, cytotoxicity and computational studies

2022

Preprint

Studies electronic structure of transition metal complexes containing metal-metal multiple bond offer insight into the nature of metal-metal bonding and facilitate predictions of the physical properties and the reactivities. In this computational study, we have explored the electronic structure of the neutral and two oxidized species of the Re2(μ-Ph2PCH2PPh2)(S2CNEt2)4 (10, 1+, and 12+) complex using state-of-the-art quantum chemical methodologies including DFT and CASSCF. In particular, we focused on the nature of the Re-Re bonding in those species. Our results show that the ground state electron configuration of the 10 is 𝜎"𝜋$𝛿"𝛿∗" with an effective bond order of 2.73 computed with CASSCF. The two oxidized processes of the 10 remove electrons from metal-based orbital as suggested by DFT to produce 1+ and 12+ with an effective bond order of 2.71 and 2.64, respectively, calculated by CASSCF. Those values very similar to that of the neutral molecule suggesting that the oxidation process has almost no effect on the Re-Re bond strength even though it remove electrons from metal-based orbitals. However, the wavefunction is different which explain the similarity of effective bond order of all three species. The electrons of the 𝛿 components of the Re-Re bond is localized on two Re ions in the 1+ and 12+ which are excluded from bond order evaluation. In another words, the 𝜎 and 𝜋 and their antibonding counterparts are determined the nature of the Re-Re bonding of the oxidized species (1+ and 12+).

Section: Resultsmentioning

confidence: 60%

Section: Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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A multiconfigurational approach to the electronic structure of electro-generated species of the Re2(μ- Ph2PCH2PPh2)(S2CNEt2)4 complex

2022

Preprint

“…These results are also in accord with previous DFT calculations. 17 Those results demonstrated that our DFT methodology is valid for investigating the electronic structure of 1 0 and it is oxidized forms (1 + and 1 2+ ). As we have mentioned above, Kohn-Sham molecular orbital diagram of 1 0 is displayed in Figure 2 comparable to that of [Re2Cl8] 2-.…”

Section: Resultsmentioning

confidence: 67%

“…4 The Re2Cl4(µ-dppm)2 complex react with different ligands to produce a variety of molecules, those ligands are, for example, dioxygen, 5 PhSeSePh, 6 2-mercaptoquinoline, 7 2-hydroxypyridine, 8 carbon disulfide, 9 sulfur dioxide, 10 triphenylguanidine, 11 and acetylacetonate, 12 carbon monoxide, isocyanides, and nitriles. 13,14,15,16 Recently, Chattopadhyay and co-worker 17 have synthesised Re2(µ-dppm)(S2CNEt2)4 (1 0 ) complex (Figure1a) starting from the Re2Cl4(µ-dppm)2. The cyclic voltammetry measurements of the Re2(µ-dppm)(S2CNEt2)4 complex display two quasi-reversible one-electron oxidation processes, the two oxidation processes in the ranges -0.022 V to -0.070 V and +1.22 V to +1.196 V are assigned to the Re2 5+ /Re2 4+ and Re2 6+ /Re2 5+ couples, respectively.…”

Section: Introductionmentioning

confidence: 99%

A multiconfigurational approach to the electronic structure of electro-generated species of the Re2(μ- Ph2PCH2PPh2)(S2CNEt2)4 complex

2022

Preprint

The nature of Re-Re bonding in Re2(µ-Ph2PCH2PPh2)(S2CNEt2)4 complex, including its neutral (10) and two oxidized (1+ and 12+) species, was explored utilizing state-of-the-art quantum chemical methodologies within density functional theory (DFT) and complete active space self-consistent field (CASSCF). Our results show that the ground state electron configuration of the 10 is σ^2 π^4 δ^2 δ^(*2) with an effective bond order (EBO) of 2.73 computed with CASSCF. The oxidation discloses an electron removal from a metal-based orbital, giving 1+ and 12+ with an EBO of 2.71 and 2.64, respectively. The relative similarity in EBO values among neutral and oxidized species suggests that the oxidation processes have almost no effect on the Re-Re bond strength even though electrons removal from metal-based orbitals because the electrons that occupied the δ components of Re-Re bonds in 1+ and 12+ localized on the two Re ions, thus, they were excluded from EBO estimation.

A multiconfigurational approach to the electronic structure of electro‐generated species of the Re₂(μ‐Ph₂PCH₂PPh₂)(S₂CNEt₂)₄ complex

Zeitschrift anorg allge chemie

2022

The nature of ReÀ Re bonding in Re 2 (μ-Ph 2 PCH 2 PPh 2 )(S 2 CNEt 2 ) 4 complex, including its neutral (1 0 ) and two oxidized (1 + and 1 2 + ) species, was explored utilizing state-of-the-art quantum chemical methodologies within density functional theory (DFT) and complete active space self-consistent field (CASSCF). Our results show that the ground state electron configuration of the 1 0 is s 2 p 4 d 2 d *2 with an effective bond order (EBO) of 2.73 computed with CASSCF. The oxidation discloses an electron removal from a metal-based orbital, giving 1 + and 1 2 + with an EBO of 2.71 and 2.64, respectively. The relative similarity in EBO values among neutral and oxidized species suggests that the oxidation processes have almost no effect on the ReÀ Re bond strength even though electrons removal from metal-based orbitals because the electrons that occupied the d components of ReÀ Re bonds in 1 + and 1 2 + localized on the two Re ions, thus, they were excluded from EBO estimation.