Group 13 complexes of dipyridylmethane, a forgotten ligand in coordination chemistry

Vasko, Petra; Kinnunen, Virva; Moilanen, Jani O.; Roemmele, Tracey L.; Boeré, René T.; Konu, Jari; Tuononen, Heikki M.

doi:10.1039/c5dt02830b

Cited by 10 publications

(11 citation statements)

References 51 publications

(42 reference statements)

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“…Furthermore, a new ligand class arose when the 2‐pyridyl residues were exchanged for benzannulated oxazoline sidearms. Despite the fact that bis(heterocyclo)methane ligands (L) can act as both neutral (LH) and monoanionic (L − ) chelates suitable for transition‐metal chemistry, they have attracted little attention in coordination chemistry so far …”

Section: Introductionmentioning

confidence: 99%

“…Despite the fact that bis(heterocyclo)methane ligands (L) can act as both neutral( LH) and monoanionic (L À )c helates suitable for transition-metal chemistry, they have attracted little attention in coordinationc hemistry so far. [34,35] Nevertheless,o ur group showed that bis(benzoxazol-2-yl)and bis(benzothiazol-2-yl)methanides are versatile platforms for Group 1a nd 13 metal complexes. [36,37] This chemistryw as extendedt ot he corresponding N-bridged derivatives [38] and, most recently,t ob enzimidazol-and asymmetrically substituted bis(heterocyclo)methane species (Scheme 2, right).…”

Section: Introductionmentioning

confidence: 99%

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A Novel Bulky Heteroaromatic‐Substituted Methanide Mimicking NacNac: Bis(4,6‐tert‐butylbenzoxazol‐2‐yl)methanide in s‐Block Metal Coordination

Koehne

Bachmann

Niklas

et al. 2017

Chemistry A European J

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A novel bulky bis(4,6-tBu-benzoxazol-2-yl)methane ligand was synthesized in a straightforward three-step synthesis. The corresponding complexes [Li{(4,6-tBu-NCOC H ) CH}THF], [K{η -(4,6-tBu-NCOC H ) CH}] , and [MgCl{(4,6-tBu-NCOC H ) CH}(THF) ] were obtained upon metalation with alkaline or alkaline-earth-metal reagents. Reduction of [MgCl{(4,6-tBu-NCOC H ) CH}(THF) ] with potassium metal or KC led to the formation of the homoleptic compound [Mg{(4,6-tBu-NCOC H ) CH} ]. All compounds were fully characterized. Their solid-state structures as well as their behavior in solution, which was analyzed with the help of advanced NMR spectroscopic techniques, are discussed in detail.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A Novel Bulky Heteroaromatic‐Substituted Methanide Mimicking NacNac: Bis(4,6‐tert‐butylbenzoxazol‐2‐yl)methanide in s‐Block Metal Coordination

Koehne

Bachmann

Niklas

et al. 2017

Chemistry A European J

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“…The latter were also extensively studied with regard to the charge demands of the corresponding heteroaryl substituents in the derived deprotonated forms . Despite the fact that bis(heterocyclo)methane ligands could act as a suitable platform for transition metal complexes because of their ability to behave as both, neutral and monoanionic ligands, they have attracted very little attention in the field of main‐group coordination chemistry over the last three decades …”

Section: Introductionmentioning

confidence: 99%

Bis(4‐methylbenzoxazol‐2‐yl)methanide in s‐Block Metal Coordination

Koehne

Herbst‐Irmer

2017

Eur J Inorg Chem

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On the basis of the bis(4‐methylbenzoxazol‐2‐yl)methanide ligand three new alkali or alkaline earth metal compounds were synthesized, and their solid‐state structures are discussed in detail. On the way to new alkaline earth metal species a promising potassium precursor complex [K{(4‐MeNCOC6H3)2CH}{η5‐K(4‐MeNCOC6H3)2CH}(THF)]∞ (2) and a homoleptic magnesium [Mg{(4‐MeNCOC6H3)2CH}2] (3) and calcium complex [Ca{(4‐MeNCOC6H3)2CH}2(THF)2]·THF (4) were obtained.

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“…The experimental BCl bond length in seven molecules with the CSD Refcode: CAQNEN, FUMXAO, ACNBCL, TUWMEF, BUGGUF, ADAJIA, and ADAJEW is between 1.793 and 1.917Å (see Tables and ).…”

Section: Resultsmentioning

confidence: 99%

The electronic structure of molecules with the BF and BCl bond in light of the topological analysis of electron localization function: Possibility of multiple bonds?

Mierzwa

Gordon

Berski

2018

Int J of Quantum Chemistry

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Topological analysis of electron localisation function (ELF) has been used to study the nature of the B X (X = F, Cl) bonds in 26 molecules. Twelve small molecules with formal B X, B X, and B X bonds and 14 organoboron molecules with the B Cl bond from the Cambridge Structural Database have been studied using CCSD, DFT(M062x) methods. As the V(B,F) basin population for the investigated molecules is smaller than 4 and 6e, the existence of B X, B X bonds is not confirmed. The results show higher polarity of B F bonds as compared to the B Cl bonds. Electronic structure of selected molecules has been discussed from the ELF-topological perspective. K E Y W O R D S B Cl, B F, chemical bond, double bond, electron localisation function, Lewis structure, QCT, quantum chemical topology, triple bond 1 | INTRODUCTION Nature of a localized, dicenter-two-electron (2c 2e) chemical bond, A-B, assumed to exist between a pair of atoms in a molecule, is one of the most important considerations of theoretical chemistry. Such bond can broadly be characterized as covalent or ionic. The concept of covalentbond is based on sharing electron densities, while ionic bond stems from electrostatic interactions. A contemporary paradigm, derived from quantum theory, states that chemical bonding can be described using the molecular orbital (MO) theory [1] or valence bond (VB) theory, [2] where covalent chemical bond between A and B is a consequence of atomic orbitals overlapping. Molecular orbitals, fully characterizing electronic structure of molecules are vectors in the Hilbert space. Notably, chemical bonding can also be described using the graph theory [3] or the information theory. [4] Another way of analyzing the nature of a chemical bond, developed in addition to the MO and VB theories, constitute of methods operating in a real (physical) space. They focus on topological properties of the scalar fields: electron density, ρ(r), [5] electron localisation function, ELF, η(r), [6,7] electron localisability indicator, ELI-D, [8] electrostatic potential, [9] and others. [10,11] All those methods have been gathered by Popelier [12] under the umbrella of quantum chemical topology (QCT).This article concentrates only on topological analysis of ELF from the whole range of the QCT, therefore, a nonexpert reader is encouraged to familiarize with the subject. [6,7,[13][14][15][16][17] In short, the two-center two-electron (2c 2e) covalent bond, A-B, is represented by an attractor (local maximum) of the η(r) field, V (A,B), found in the region of expected chemical bond. The attractor V(A,B) belongs to valence and disynaptic types. [13,18] Futher application of the gradient vector theory of dynamical systems enables calculation of its basin (localisation basin) for ELF, denoted also V (A,B). Projection of all points of η(r) field, defining attractor's basin in the electron density field, ρ(r) and integrating the electron density with respect to the localisation basin leads to the definition of its basin population, N. Further analysis includes d...

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Group 13 complexes of dipyridylmethane, a forgotten ligand in coordination chemistry

Cited by 10 publications

References 51 publications

A Novel Bulky Heteroaromatic‐Substituted Methanide Mimicking NacNac: Bis(4,6‐tert‐butylbenzoxazol‐2‐yl)methanide in s‐Block Metal Coordination

A Novel Bulky Heteroaromatic‐Substituted Methanide Mimicking NacNac: Bis(4,6‐tert‐butylbenzoxazol‐2‐yl)methanide in s‐Block Metal Coordination

Bis(4‐methylbenzoxazol‐2‐yl)methanide in s‐Block Metal Coordination

The electronic structure of molecules with the BF and BCl bond in light of the topological analysis of electron localization function: Possibility of multiple bonds?

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