Chemical bonding in transition metal carbonyl clusters: complementary analysis of theoretical and experimental electron densities.

Macchi, Piero; Sironi, Angelo

doi:10.1016/s0010-8545(02)00252-7

Cited by 678 publications

(713 citation statements)

References 98 publications

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“…Similar BCP characteristics have been found in transition-metal carbonyl complexes in which the π back-donating character of the bonds dominates. [59][60][61] In the case of the NO ligand, the values of ρ BCP and ٌ 2 ρ BCP are more similar to the NO radical than to NO + , which is in agreement with the QTAIM charges as well as the bond lengths. The BCP ellipticities of Ru-Cl1 and Ru-N3 in 1 are close to zero, which is in agreement with the axial symmetry of these bonds.…”

Section: Qtaim Analysissupporting

confidence: 66%

On the Electronic Structure ofmer,trans‐[RuCl₃(1H‐indazole)₂(NO)], a Hypothetical Metabolite of the Antitumor Drug Candidate KP1019: An Experimental and DFT Study

et al. 2013

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The study reported herein focused on the electronic structure of the {Ru(NO)} 6 fragment and characterization of the oxidation state of ruthenium in mer,trans- [RuCl 3 (Hind) (3) were experimentally and theoretically investigated as reference compounds. A complete active space SCF calculation was performed to estimate the extent of antiferromagnetic spin-spin coupling in 1. We found that the closed-shell structure {Ru III (NO) 0 } 6 fits better to the physical/ spectroscopic properties of 1, although {Ru II (NO) + } 6 is formally still suitable for describing the oxidation state of Ru in this entity.

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Section: Qtaim Analysissupporting

confidence: 66%

On the Electronic Structure ofmer,trans‐[RuCl₃(1H‐indazole)₂(NO)], a Hypothetical Metabolite of the Antitumor Drug Candidate KP1019: An Experimental and DFT Study

et al. 2013

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“…35 eÅ 5 for its Laplacian ( 2 ), which is a feature characteristic of multiple CO bonds in organic molecules and transition-metal carbonyls. 11 In contrast, the PO bond for the Mo-bound O atom displays a lower electron density at the corresponding bcp (1.240 eÅ 3 ), with a negative value for its Laplacian (17.6 eÅ 5 ), as expected for a covalent single bond.…”

Section: Synthesis and Structure Of Dioxo-and Thiooxophosphorane Compmentioning

confidence: 93%

Nucleophilic behaviour of dioxo- and thiooxophosphorane complexes [MoCp(CO)₂{E,P-EP(O)(2,4,6-C₆H₂^tBu₃)}]⁻(E = O, S)

et al. 2014

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ARTICLEThe structure of two of these products (X = C(O)C 2 H 3 , SiMe 3 ) was determined by single-crystal X-ray diffraction studies. Density functional theory (DFT) calculations of the title anions and some of their derivatives indicated that attachment of an external electrophile to the terminal O atom of the thiooxophosphorane ligand is favoured under conditions of charge control, while the sulphur atom is the favoured site under conditions of orbital control, although it leads to less stable products. IntroductionDioxophosphoranes (RPO 2 ) and thiooxophosphoranes (RPOS) are unstable molecules generated during thermolysis of a great variety of suitable organophosphorus precursors. These transient molecules display a strongly electrophilic character located at their positively-polarized phosphorus(V) atom, this enabling their use as strong phosphorylating agents upon reaction with many different organic substrates while, in the absence of external reagents, they usually evolve through polymerization or intramolecular activation of CH bonds. 1 Only under very favourable conditions can these species be detected directly, as it is the case of MePO 2 when generated in the gas phase under high vacuum. 2 It might be conceived that substantial stabilization of these elusive molecules could be achieved through coordination to metal centres, which in turn would allow for a more detailed study of their chemical behaviour. However, the coordination chemistry of these molecules is virtually unknown, with just one example described for a dioxophosphorane complex. 3 In a preliminary study we found that the anionic oxophosphinidene complex (H-(1), (R* = 2,4,6-C 6 H 2 t Bu 3 ; Cp= and thiooxophosphorane (H-DBU)[MoCp(CO) 2 {S,P-SP(O)R*}] (3) derivatives (Scheme 1). 4 Because of the negative charge of the latter complexes, the acid-base chemistry of their phosphorus ligands is reversed, so they can now behave as nucleophiles. Indeed our preliminary study on the reactivity of the thiooxophosphorane complex 3 indicated that methylation could occur easily at either the S and O sites, to give unprecedented thiolophosphinide (PR(O)(SMe)) and phosphonothiolate (PR(OMe)S) derivatives, respectively. 4 Therefore it was of interest exploring the potential of anions 2 and 3 in the generation of novel P-donor entities. In this paper we give full details of the above reactions, which we have now extended to the dioxophosphorane complex 2 and also to other electrophilic reagents, including the proton and some metalbased electrophiles. As it will be shown, most electrophiles add to the terminal oxygen atom of the phosphorus ligand of the above anions, an event favoured on steric, electrostatic and thermodynamic grounds, according to our theoretical calculations. Addition to the sulphur site of the thiooxophosphorane ligand is an orbital-favoured event only observed in the methylation reactions of 3. Scheme 1Results and Discussion Synthesis and structure of dioxo-and thiooxophosphorane complexesThe oxophosphinidene complex 1 reacts readily at...

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“…One of the most well known donation/back-donation scheme is that proposed by Dewar, Chatt, and Duncanson (DCD) 21,22 widely adopted to explain bonding in metal olefins [34][35][36][37] or metal carbonyl complexes. [38][39][40][41][42][43][44][45] As the M-CO bond is regarded, and grossly speaking in standard orbital parlance, a s-donation from the HOMO of CO into an empty orbital of M is accompanied by p-backdonation from a d orbital of M into the LUMO of CO. Such a simple model explains a large set of experimental facts, and even though it has been questioned many times, particularly after the discovery of non-classical carbonyls [45][46][47] with CO stretching frequencies larger than those of free CO, it has essentially survived up-to-date.…”

Section: Selected Examples and Computational Detailsmentioning

confidence: 99%

Restoring orbital thinking from real space descriptions: bonding in classical and non-classical transition metal carbonyls

Tiana

Francisco

Blanco

et al. 2011

Phys. Chem. Chem. Phys.

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A combined strategy that unifies our interacting quantum atoms approach (IQA), a chemically intuitive energetic perspective within the quantum theory of atoms in molecules (QTAIM), the domain natural orbitals obtained by the diagonalization of the charge-weighted domain-averaged Fermi hole (DAFH), and the statistical analyses of chemical bonding provided by the electron number distribution functions (EDF) is presented. As shown, it allows for recovering traditional orbital images from the orbital invariant descriptions of QTAIM. It does also provide bonding indices (like bond orders) and bond energetics, all in a per orbital basis, still invariant manner, using a single unified framework. The procedure is applied to show how the Dewar, Chatt, and Ducanson model of bonding in simple transition metal carbonyls may be recovered in the real space. The balance between the number of s-donated and p-backdonated electrons is negative in classical compounds and positive in non-classical ones. The energetic strength of backdonation is, however, smaller than that of donation. Our technique surpasses conventional orbital models by providing physically sound, quantitative energetics of chemical bonds (or interactions) together with effective one-electron pictures, all for arbitrary wavefunctions.

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Chemical bonding in transition metal carbonyl clusters: complementary analysis of theoretical and experimental electron densities.

Cited by 678 publications

References 98 publications

On the Electronic Structure ofmer,trans‐[RuCl₃(1H‐indazole)₂(NO)], a Hypothetical Metabolite of the Antitumor Drug Candidate KP1019: An Experimental and DFT Study

On the Electronic Structure ofmer,trans‐[RuCl₃(1H‐indazole)₂(NO)], a Hypothetical Metabolite of the Antitumor Drug Candidate KP1019: An Experimental and DFT Study

Nucleophilic behaviour of dioxo- and thiooxophosphorane complexes [MoCp(CO)₂{E,P-EP(O)(2,4,6-C₆H₂^tBu₃)}]⁻(E = O, S)

Restoring orbital thinking from real space descriptions: bonding in classical and non-classical transition metal carbonyls

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Chemical bonding in transition metal carbonyl clusters: complementary analysis of theoretical and experimental electron densities.

Cited by 678 publications

References 98 publications

On the Electronic Structure ofmer,trans‐[RuCl3(1H‐indazole)2(NO)], a Hypothetical Metabolite of the Antitumor Drug Candidate KP1019: An Experimental and DFT Study

On the Electronic Structure ofmer,trans‐[RuCl3(1H‐indazole)2(NO)], a Hypothetical Metabolite of the Antitumor Drug Candidate KP1019: An Experimental and DFT Study

Nucleophilic behaviour of dioxo- and thiooxophosphorane complexes [MoCp(CO)2{E,P-EP(O)(2,4,6-C6H2tBu3)}]−(E = O, S)

Restoring orbital thinking from real space descriptions: bonding in classical and non-classical transition metal carbonyls

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On the Electronic Structure ofmer,trans‐[RuCl₃(1H‐indazole)₂(NO)], a Hypothetical Metabolite of the Antitumor Drug Candidate KP1019: An Experimental and DFT Study

On the Electronic Structure ofmer,trans‐[RuCl₃(1H‐indazole)₂(NO)], a Hypothetical Metabolite of the Antitumor Drug Candidate KP1019: An Experimental and DFT Study

Nucleophilic behaviour of dioxo- and thiooxophosphorane complexes [MoCp(CO)₂{E,P-EP(O)(2,4,6-C₆H₂^tBu₃)}]⁻(E = O, S)