Topological analysis of the metal-metal bond: A tutorial review

Lepetit, Christine; Fau, Pierre; Fajerwerg, Katia; Kahn, Myrtil L.; Silvi, Bernard

doi:10.1016/j.ccr.2017.04.009

Cited by 119 publications

(112 citation statements)

References 331 publications

(407 reference statements)

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“…More important, quantities related to the strength of the bonds such as the electron density ρ and the potential energy density V remained almost constant on changing the carbene ligand from IMes to IPr. The negative values of energy densities E and the positive values for the Laplacian of electron density ∇ 2 ρ agreed with Bianchi′s definitions of dative M–M bonds , …”

Section: Computational Studiessupporting

confidence: 79%

Synthesis and Characterization of Heterobimetallic Carbonyl Clusters with Direct Au‐Fe and Au···Au Interactions Supported byN‐Heterocyclic Carbene and Phosphine Ligands

et al. 2019

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The reaction of Collman's reagent Na 2 [Fe(CO) 4 ]·2thf with one equivalent of Au(NHC)Cl (NHC = IMes, IPr; IMes = C 3 N 2 H 2 (C 6 H 2 Me 3 ) 2 ; IPr = C 3 N 2 H 2 (C 6 H 3 iPr 2 ) 2 ) in dmso resulted in the [Fe(CO) 4 (AuNHC)] -(NHC = IMes, 1; IPr, 2) mono-anions. 1-2 further reacted with Au(NHC)Cl or Au(PPh 3 )Cl affording the neutral complexes Fe(CO) 4 (AuNHC) 2 (NHC = IMes, 3; IPr, 4), Fe(CO) 4 (AuIMes)(AuIPr) (5) and Fe(CO) 4 (AuNHC)(AuPPh 3 ) (NHC = IMes, 6; IPr, 7). 1-7 have been spectroscopically characterized by IR, 1 H, 13 C{ 1 H} and 31 P{ 1 H} NMR techniques. Moreover, the molecular structures of 1, 2, 4, 6 and 7 have been determined through single-crystal X-ray diffraction as their [NMe 4 ][Fe(CO) 4 -[a] Dipartimento

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Section: Computational Studiessupporting

confidence: 79%

Synthesis and Characterization of Heterobimetallic Carbonyl Clusters with Direct Au‐Fe and Au···Au Interactions Supported byN‐Heterocyclic Carbene and Phosphine Ligands

et al. 2019

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“…According to Espinosa et al [51], the ratio H(rb)/ρ(rb) can be utilized as a covalence degree parameter (for systems where d < dcov, |V(rb)| > G(rb), H(rb) < 0), the greater magnitude of which indicates the stronger atom-atom interaction (leading to an order of increasing strength 2 < 3 < 1). For the series under investigation, the analysis of the estimated interaction energies (Eint) [52,53] Furthermore, for the paramagnetic compound 3, this analysis afforded a Mulliken spin density distribution of 65.9% Cu-localization and 6.9-7.3%, located at each of the four nitrogen atoms. This is in accordance with the ligand field theory, which would assign the unpaired electron of a d 9 system As the TM-Si interactions in compounds 1 and especially in 2 and 3 appear to be of an electrostatic/polar nature rather than covalent, the non-covalent interactions (NCI) descriptor of these compounds was analyzed (Figure 4).…”

Section: Reactions Of Mesi(pyo)3 With [Pdcl2(ncme)2] and Cuclmentioning

confidence: 99%

mentioning

confidence: 98%

(2-Pyridyloxy)silanes as Ligands in Transition Metal Coordination Chemistry

et al. 2018

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Proceeding our initial studies of compounds with formally dative TM→Si bonds (TM = Ni, Pd, Pt), which feature a paddlewheel arrangement of four (N,S) or (N,N) bridging ligands around the TM–Si axis, the current study shows that the (N,O)-bidentate ligand 2-pyridyloxy (pyO) is also capable of bridging systems with TM→Si bonds (shown for TM = Pd, Cu). Reactions of MeSi(pyO)3 with [PdCl2(NCMe)2] and CuCl afforded the compounds MeSi(µ-pyO)4PdCl (1) and MeSi(µ-pyO)3CuCl (2), respectively. In the latter case, some crystals of the Cu(II) compound MeSi(µ-pyO)4CuCl (3) were obtained as a byproduct. Analogous reactions of Si(pyO)4, in the presence of HpyO, with [PdCl2(NCMe)2] and CuCl2, afforded the compounds [(HpyO)Si(µ-pyO)4PdCl]Cl (4), (HpyO)2Si[(µ-pyO)2PdCl2]2 (5), and (HpyO)2Si[(µ-pyO)2CuCl2]2 (6), respectively. Compounds 1–6 and the starting silanes MeSi(pyO)3 and Si(pyO)4 were characterized by single-crystal X-ray diffraction analyses and, with exception of the paramagnetic compounds 3 and 6, with NMR spectroscopy. Compound 2 features a pentacoordinate Si atom, the Si atoms of the other complexes are hexacoordinate. Whereas compounds 1–4 feature a TM→Si bond each, the Si atoms of compounds 5 and 6 are situated in an O6 coordination sphere, while the TMCl2 groups are coordinated to pyridine moieties in the periphery of the molecule. The TM–Si interatomic distances in compounds 1–4 are close to the sum of the covalent radii (1 and 4) or at least significantly shorter than the sum of the van-der-Waals radii (2 and 3). The latter indicates a noticeably weaker interaction for TM = Cu. For the series 1, 2, and 3, all of which feature the Me–Si motif trans-disposed to the TM→Si bond, the dependence of the TM→Si interaction on the nature of TM (Pd(II), Cu(I), and Cu(II)) was analyzed using quantum chemical calculations, that is, the natural localized molecular orbitals (NLMO) analyses, the non-covalent interaction (NCI) descriptor, Wiberg bond order (WBO), and topological characteristics of the bond critical points using the atoms in molecules (AIM) approach.

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“…In Lewis's theory, the synaptic order is one for the non-bonding pairs and two for the bonding ones. Values larger than two enable to account for multicentre bonds and particularly for interstitial multicentre partial bond representation of bulk metals [62][63][64].…”

Section: Testing the Hypotheses Of The Lewis's And Vsepr Models With mentioning

confidence: 99%

About Lewis’s heritage: chemical interpretations and quantum chemistry

Silvi

2017

Theor Chem Acc

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complementary because each of them partially addresses the question. However, other answers can be given. For instance, one can object that bottles being made to store liquid food (wine, beer), coloured glass is chosen mostly because it prevents sunlight to downgrade the antioxidants and therefore increases the storage life. 1 The answer given by the chemist explicitly invokes the chemical composition of the glass used to make bottles and for this reason it should be referred to as a chemical explanation. Chemical explanations are grounded on the knowledge of Chemistry. Chemical explanations of the structure of the matter rely on a picture in which elemental atoms are linked by bonds. Bonding interactions are moreover ruled by the location of the constituting elements in the periodic table. Chemical explanations often make use concepts proper to Chemistry, such as those of bond, lone pair, valence,..., which have been criticized as lacking of scientific content or have not enough precise or inconsistent definitions. (cf. R. Thom in Paraboles et Catastrophes [2]), We are often faced to a demarcation problem: to what extend chemical explanations are scientific explanations or in other words what are the requirements which must be fulfilled to make a chemical explanation a scientific explanation. Therefore, explanations have to be critically analysed from different epistemological viewpoints such as Duhemian conventionalism and methodological falsificationism. We must also be conscious that chemical explanations may have different structures: for example the occurrence of an event can be deduced from a set of true Abstract Some of the opinions I have on the description of the structure of the matter in chemistry. Keywords Representation of the matter • Lewis's model • VSEPR • Epistemology Published as part of the special collection of articles "First European Symposium on Chemical Bonding".

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Topological analysis of the metal-metal bond: A tutorial review

Cited by 119 publications

References 331 publications

Synthesis and Characterization of Heterobimetallic Carbonyl Clusters with Direct Au‐Fe and Au···Au Interactions Supported byN‐Heterocyclic Carbene and Phosphine Ligands

Synthesis and Characterization of Heterobimetallic Carbonyl Clusters with Direct Au‐Fe and Au···Au Interactions Supported byN‐Heterocyclic Carbene and Phosphine Ligands

(2-Pyridyloxy)silanes as Ligands in Transition Metal Coordination Chemistry

About Lewis’s heritage: chemical interpretations and quantum chemistry

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