Two octahedral σ-borane metal (MnI and RuII) complexes containing a tripod κ3N,H,H-ligand: Synthesis, structural characterization, and theoretical topological study of the charge density

Maelen, Juan F. Van der; Brugos, Javier; García‐Álvarez, Pablo; Cabeza, Javier A.

doi:10.1016/j.molstruc.2019.127217

Cited by 11 publications

(7 citation statements)

References 74 publications

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“…The presence of one BCP of Ru–H in 3 and 4 is consistent with the Wiberg bond indices (WBI) (0.310 for Ru1–H4X and 0.219 for Ru1–H3X in 3 and 0.254 for Ru1–H2X and 0.202 for Ru1–H1X in 4 ) that demonstrate inequivalent and weak interactions. Although the QTAIM analysis of 3 and 4 does not show a BCP for the Ru–B interaction, the WBI values for 3 (0.401) and 4 (0.361) indicate reasonable bonding interactions. , All of the bond properties of 2 and 3 at the selected BCPs are given in Table S4.…”

Section: Results and Discussionmentioning

confidence: 99%

Cooperative B–H and Si–H Bond Activations by κ²-N,S-Chelated Ruthenium Borate Complexes

et al. 2021

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Cooperative E–H (E = B, Si) bond activations employing κ2-N,S-chelated ruthenium borate species, [PPh3{κ2-N,S-(NS2C7H4)}Ru{κ3-H,S,S′-H2B(NC7H4S2)2}], (1) are established. Treatment of 1 with BH3·SMe2 yielded the six-membered ruthenaheterocycle [PPh3{κ2-S,H-(BH3NS2C7H4)}Ru{κ3-H,S,S’-H2B(C7H4NS2)2}] (2) formed by a hemilabile ring opening of a Ru–N bond and capturing of a BH3 unit coordinated in an “end-on” fashion. On the other hand, the bulky borane H2BMes shows different reactivity with 1 that led to the formation of the two dihydroborate complexes [{κ3-S,H,H-(NBH2Mes)(S2C7H4)}Ru{κ3-H,S,S’-H2B(C7H4NS2)2}] (3) and [PPh3{κ3-S,H,H-(NBH2Mes)(S2C7H4)}Ru(κ2-N,S-C7H4NS2)] (4), in which H2BMes has been inserted into the Ru–N bond of the initial κ2-N,S-chelated ligand. In an attempt to directly activate hydrosilanes by 1, reactions were carried out with H2SiPh2 that yielded two isomeric five-membered ruthenium silyl complexes, namely [PPh3{κ2-S,Si-(NSiPh2)(S2C7H4)}Ru{κ3-H,S,S’-H2B(C7H4NS2)2}] (5a,b), and the hydridotrisilyl complex [Ru(H){κ2-S,Si-(SiPh2NC7H4S2}3] (6). These complexes were generated by Si–H bond activation with the release of H2 and the formation of N–Si and Ru–Si bonds. When the reaction of 1 was carried out in the presence of PhSiH3, the reaction only produced the analogous complexes [PPh3{κ2-S,Si-(NSiPhH)(S2C7H4)}Ru{κ3-H,S,S’-H2B(C7H4NS2)2}] (5a′,b′). Density functional theory (DFT) calculations have been used to probe the bonding modes of boranes/silane with the ruthenium center.

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Section: Results and Discussionmentioning

confidence: 99%

Cooperative B–H and Si–H Bond Activations by κ²-N,S-Chelated Ruthenium Borate Complexes

et al. 2021

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“… 58 − 61 An earlier study by Pendás and co-workers using the IQA (Interacting Quantum Atoms) method 55 , 56 , 62 showed that the results of the IQA calculations basically support the DCD model concerning the relevance of π-backdonation for the red-shift of the C–O stretching frequencies in carbonyl complexes, but the calculated values of the delocalization indices (DI) suggest a possible multicenter bonding among the ligands in some carbonyl complexes such as [V(CO) 6 ] − , Cr(CO) 6 , and [Fe(CO) 6 ] 2+ . 58 − 60 Since the DI values of the alkaline earth octacarbonyls deviate even stronger from those of classical carbonyl complexes, Van der Maelen concluded that the DCD model is not valid for the M–CO interactions in M(CO) 8 (M = Ca, Sr, Ba). 51 …”

Section: Introductionmentioning

confidence: 99%

“…Landis and co-workers questioned the method of bonding analysis and suggested that the alkaline earth octacarbonyls are mainly bonded by ionic interactions between M 2+ and [(CO) 8 ] 2– . , Koch and co-workers challenged the interpretation of the red-shift of the CO stretching frequencies of Ca(CO) 8 in terms of π-backbonding from the d AOs of calcium, because calculations of the complex without d AOs of Ca reproduce the stretching frequencies quite well. − Van der Maelen also disputed the relevance of the d AOs of Ca, Sr, Ba for the M → (CO) 8 π-backdonation and suggests that the red-shift of the CO stretching frequencies is instead due to interligand interactions between the CO ligands . The arguments of the author are based on real-space partitioning methods, − which had previously been used for analyzing the nature of metal–CO interactions in transition metal complexes. − An earlier study by Pendás and co-workers using the IQA (Interacting Quantum Atoms) method ,, showed that the results of the IQA calculations basically support the DCD model concerning the relevance of π-backdonation for the red-shift of the C–O stretching frequencies in carbonyl complexes, but the calculated values of the delocalization indices (DI) suggest a possible multicenter bonding among the ligands in some carbonyl complexes such as [V(CO) 6 ] − , Cr(CO) 6 , and [Fe(CO) 6 ] 2+ . − Since the DI values of the alkaline earth octacarbonyls deviate even stronger from those of classical carbonyl complexes, Van der Maelen concluded that the DCD model is not valid for the M–CO interactions in M(CO) 8 (M = Ca, Sr, Ba). …”

Section: Introductionmentioning

confidence: 99%

Metal–CO Bonding in Mononuclear Transition Metal Carbonyl Complexes

Frenking

Fernández

Holzmann

et al. 2021

JACS Au

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DFT calculations have been carried out for coordinatively saturated neutral and charged carbonyl complexes [M(CO) n ] q where M is a metal atom of groups 2–10. The model compounds M(CO) 2 (M = Ca, Sr, Ba) and the experimentally observed [Ba(CO)] + were also studied. The bonding situation has been analyzed with a variety of charge and energy partitioning approaches. It is shown that the Dewar–Chatt–Duncanson model in terms of M ← CO σ-donation and M → CO π-backdonation is a valid approach to explain the M–CO bonds and the trend of the CO stretching frequencies. The carbonyl ligands of the neutral complexes carry a negative charge, and the polarity of the M–CO bonds increases for the less electronegative metals, which is particularly strong for the group 4 and group 2 atoms. The NBO method delivers an unrealistic charge distribution in the carbonyl complexes, while the AIM approach gives physically reasonable partial charges that are consistent with the EDA-NOCV calculations and with the trend of the C–O stretching frequencies. The AdNDP method provides delocalized MOs which are very useful models for the carbonyl complexes. Deep insight into the nature of the metal–CO bonds and quantitative information about the strength of the [M] ← (CO) 8 σ-donation and [M(d)] → (CO) 8 π-backdonation visualized by the deformation densities are provided by the EDA-NOCV method. The large polarity of the M–CO π orbitals toward the CO end in the alkaline earth octacarbonyls M(CO) 8 (M = Ca, Sr, Ba) leads to small values for the delocalization indices δ(M–C) and δ(M···O) and significant overlap between adjacent CO groups, but the origin of the charge migration and the associated red-shift of the C–O stretching frequencies is the [M(d)] → (CO) 8 π-backdonation. The heavier alkaline earth metals calcium, strontium and barium use their s/d valence orbitals for covalent bonding. They are therefore to be assigned to the transition metals.

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“…due to the cylindrical symmetry of the density for the Os-CO bond path, which obscures any vestige of plans. 31,32 .…”

Section: Delocalization Indicesmentioning

confidence: 99%

QTAIM analysis for Metal - Metal and Metal- Non-metal Bonds in Tri-Osmium cluster

Shatha Raheem Helal Alhimidi,

Manal A. Mohammed Al-Jabery,

Nadia Ezzat Alkurbasy

et al. 2023

J. K. Chem. Sci.

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Electron density of the interaction of the compound's chemical bonding has been computed using topological analysis. The findings suggest that Os-Os, Os-N, and Os-H bonds have experienced bond critical points (BCP) with corresponding bonds paths (BP). The presence of N-C bridging atoms is significantly impacted by electron density of Os2-Os3 bond distribution therefore no critical point found and bond path. So, due to their positive electron density (b), negative laplacian 2(b), and positive the total energy density H(b) values, the Os-NC, Os-H, and Os-CO bonds all have transit closed-shell topological properties.

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Two octahedral σ-borane metal (MnI and RuII) complexes containing a tripod κ3N,H,H-ligand: Synthesis, structural characterization, and theoretical topological study of the charge density

Cited by 11 publications

References 74 publications

Cooperative B–H and Si–H Bond Activations by κ²-N,S-Chelated Ruthenium Borate Complexes

Cooperative B–H and Si–H Bond Activations by κ²-N,S-Chelated Ruthenium Borate Complexes

Metal–CO Bonding in Mononuclear Transition Metal Carbonyl Complexes

QTAIM analysis for Metal - Metal and Metal- Non-metal Bonds in Tri-Osmium cluster

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Two octahedral σ-borane metal (MnI and RuII) complexes containing a tripod κ3N,H,H-ligand: Synthesis, structural characterization, and theoretical topological study of the charge density

Cited by 11 publications

References 74 publications

Cooperative B–H and Si–H Bond Activations by κ2-N,S-Chelated Ruthenium Borate Complexes

Cooperative B–H and Si–H Bond Activations by κ2-N,S-Chelated Ruthenium Borate Complexes

Metal–CO Bonding in Mononuclear Transition Metal Carbonyl Complexes

QTAIM analysis for Metal - Metal and Metal- Non-metal Bonds in Tri-Osmium cluster

Contact Info

Product

Resources

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Cooperative B–H and Si–H Bond Activations by κ²-N,S-Chelated Ruthenium Borate Complexes

Cooperative B–H and Si–H Bond Activations by κ²-N,S-Chelated Ruthenium Borate Complexes