Carbones and Carbon Atom as Ligands in Transition Metal Complexes

Zhao, Lili; Chai, Chaoqun; Petz, Wolfgang; Frenking, Gernot

doi:10.3390/molecules25214943

Cited by 53 publications

(42 citation statements)

References 143 publications

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“…Examples for such ligands are carbones CL 2 [6] and the heavier group‐14 tetrylones EL 2 (E=Si–Sn), [7] where the ligands L are bonded to a divalent atom C or E in the electronic 1 D state with the four valence electrons occupying two lone‐pair orbitals with σ and π symmetry [8] . Complexes with tetrylone ligands are experimentally known [9] and their bonding situation was studied with theoretical methods [10]…”

Section: Introductionmentioning

confidence: 99%

Chemical Bonding in Homoleptic Carbonyl Cations [M{Fe(CO)₅}₂]⁺(M=Cu, Ag, Au)

Pan

Gorantla

Parasar

et al. 2021

Chemistry A European J

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Syntheses of the copper and gold complexes [Cu{Fe(CO)5}2][SbF6] and [Au{Fe(CO)5}2][HOB{3,5‐(CF3)2C6H3}3] containing the homoleptic carbonyl cations [M{Fe(CO)5}2]+ (M=Cu, Au) are reported. Structural data of the rare, trimetallic Cu2Fe, Ag2Fe and Au2Fe complexes [Cu{Fe(CO)5}2][SbF6], [Ag{Fe(CO)5}2][SbF6] and [Au{Fe(CO)5}2][HOB{3,5‐(CF3)2C6H3}3] are also given. The silver and gold cations [M{Fe(CO)5}2]+ (M=Ag, Au) possess a nearly linear Fe‐M‐Fe’ moiety but the Fe‐Cu‐Fe’ in [Cu{Fe(CO)5}2][SbF6] exhibits a significant bending angle of 147° due to the strong interaction with the [SbF6]− anion. The Fe(CO)5 ligands adopt a distorted square‐pyramidal geometry in the cations [M{Fe(CO)5}2]+, with the basal CO groups inclined towards M. The geometry optimization with DFT methods of the cations [M{Fe(CO)5}2]+ (M=Cu, Ag, Au) gives equilibrium structures with linear Fe‐M‐Fe’ fragments and D2 symmetry for the copper and silver cations and D4d symmetry for the gold cation. There is nearly free rotation of the Fe(CO)5 ligands around the Fe‐M‐Fe’ axis. The calculated bond dissociation energies for the loss of both Fe(CO)5 ligands from the cations [M{Fe(CO)5}2]+ show the order M=Au (De=137.2 kcal mol−1)>Cu (De=109.0 kcal mol−1)>Ag (De=92.4 kcal mol−1). The QTAIM analysis shows bond paths and bond critical points for the M−Fe linkage but not between M and the CO ligands. The EDA‐NOCV calculations suggest that the [Fe(CO)5]→M+←[Fe(CO)5] donation is significantly stronger than the [Fe(CO)5]←M+→[Fe(CO)5] backdonation. Inspection of the pairwise orbital interactions identifies four contributions for the charge donation of the Fe(CO)5 ligands into the vacant (n)s and (n)p AOs of M+ and five components for the backdonation from the occupied (n‐1)d AOs of M+ into vacant ligand orbitals.

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Section: Introductionmentioning

confidence: 99%

Chemical Bonding in Homoleptic Carbonyl Cations [M{Fe(CO)₅}₂]⁺(M=Cu, Ag, Au)

Pan

Gorantla

Parasar

et al. 2021

Chemistry A European J

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“…Carbodiphosphoranes (CDPs) with the general composition (R 3 P) 2 C can be interpreted as ligand-stabilized carbon(0) compounds with two electron lone pairs mainly located at the central carbon atom. [1][2][3][4] This description of the bonding situation is underlined by their ability to act as σand π-donor ligands [5][6][7][8] as well as μ 2 -bridging ligands in transition metal complexes [9,10] and between main group element Lewis acids. [11] In this context, CDPs were shown to be strong electron donating ligands, [12,13] which are suited to stabilize transition metal ions over a wide range formal oxidation states.…”

Section: Introductionmentioning

confidence: 99%

Facial vs. Meridional Coordination Modes in Re^I Tricarbonyl Complexes with a Carbodiphosphorane‐based Tridentate Ligand

Maser

Vogt

Langer

2021

Zeitschrift anorg allge chemie

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The reactivity of the novel cationic ligand precursor [(dppm)2CH](PF6) (1) with a weakly coordinating anion and [ReBr(CO)5] is reported. The initial coordination results in the formation of the facially coordinated dicationic complex fac‐[({dppm}2CH)Re(CO)3]X2 (fac‐2, X=Br, PF6). The facial coordination mode is retained in fac‐[({dppm}2C)Re(CO)3](PF6) (fac‐3) upon deprotonation of the central cationic donor group. Quantum chemical investigations indicate that for both complexes, 2 and 3, the meridional coordination mode is thermodynamically favored. In line with these findings, the isomerization of the facially coordinated complex fac‐3 to the meridionally coordinated complex mer‐[({dppm}2C)Re(CO)3](PF6) (mer‐3) is observed under irradiation with UV‐light.

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“…This deficiency has been overcome by the introduction of negative charge in the backbone leading to the triphosphenium zwitterion 20 (Scheme 11). [59–61] Such P(I) systems having overall electroneutrality were able to mono‐ or di‐coordinate transition metals (Scheme 11), [59–61] analogous to the coordination chemistry of carbones [20] …”

Section: Phosphorous(i) Cationmentioning

confidence: 99%

Recent Developments in the Chemistry of Pn(I) (Pn=N, P, As, Sb, Bi) Cations

Majumdar

Deb

Balakrishna

2021

Chemistry An Asian Journal

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The Group 15 Pn(I) cations (Pn=N, P, As, Sb and Bi), which are isoelectronic with the donor‐stabilized carbones, have emerged recently. Despite the presence of two lone pair of electrons, the Pn(I) cations are weakly nucleophilic due to their inherent positive charge. Strongly electron‐donating supporting ligands including zwitterionic forms have been used to enhance their Lewis basicity. Furthermore, the chelating effect of cyclic ligand systems proved effective in increasing their nucleophilicity. The strategies involved in successfully isolating the fleeting Sb(I) and Bi(I) cations as the recent most achievements in this field have been discussed. The syntheses, structure, bonding situations and reactivity of the Pn(I) cations are discussed. An outlook on the periodic trends and future applications of these electronically unique electron‐rich cationic moieties have been provided.

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Carbones and Carbon Atom as Ligands in Transition Metal Complexes

Cited by 53 publications

References 143 publications

Chemical Bonding in Homoleptic Carbonyl Cations [M{Fe(CO)₅}₂]⁺(M=Cu, Ag, Au)

Chemical Bonding in Homoleptic Carbonyl Cations [M{Fe(CO)₅}₂]⁺(M=Cu, Ag, Au)

Facial vs. Meridional Coordination Modes in Re^I Tricarbonyl Complexes with a Carbodiphosphorane‐based Tridentate Ligand

Recent Developments in the Chemistry of Pn(I) (Pn=N, P, As, Sb, Bi) Cations

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Carbones and Carbon Atom as Ligands in Transition Metal Complexes

Cited by 53 publications

References 143 publications

Chemical Bonding in Homoleptic Carbonyl Cations [M{Fe(CO)5}2]+(M=Cu, Ag, Au)

Chemical Bonding in Homoleptic Carbonyl Cations [M{Fe(CO)5}2]+(M=Cu, Ag, Au)

Facial vs. Meridional Coordination Modes in ReI Tricarbonyl Complexes with a Carbodiphosphorane‐based Tridentate Ligand

Recent Developments in the Chemistry of Pn(I) (Pn=N, P, As, Sb, Bi) Cations

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Chemical Bonding in Homoleptic Carbonyl Cations [M{Fe(CO)₅}₂]⁺(M=Cu, Ag, Au)

Chemical Bonding in Homoleptic Carbonyl Cations [M{Fe(CO)₅}₂]⁺(M=Cu, Ag, Au)

Facial vs. Meridional Coordination Modes in Re^I Tricarbonyl Complexes with a Carbodiphosphorane‐based Tridentate Ligand