An experimental and DFT computational study of a novel zerovalent tetracarbonyl tungsten complex of 2-(2′-pyridyl)quinoxaline

Veroni, Irene; Makedonas, Christodoulos; Rontoyianni, Aliki; Mitsopoulou, Christiana A.

doi:10.1016/j.jorganchem.2005.07.023

Cited by 29 publications

(39 citation statements)

References 70 publications

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“…In such a molecule, bending of the CO ligands should be clear and free from the difficult to describe nonorthogonal dihedral angles, as in the case of W(CO) 4 (pq) [pq = 2-(2Ј-pyridyl)-quinoxaline] where the calculated dihedral angle forN py -N qn -W-C ax is -92.6°. [5] In the literature, three crystal structures exist as reported in ref.…”

Section: Evolution Of Back-donation In W(co) 4 (Phen)mentioning

confidence: 99%

“…[5] At this point we should emphasize that mixing of frontier orbitals is an important parameter of the system and is connected to the negative solvatochromism and the existence of NLO properties for these types of compounds.…”

Section: Evolution Of Back-donation In W(co) 4 (Phen)mentioning

confidence: 99%

“…This state arises from the transition between a metal/CO localized HOMO-2 and a diimine LUMO (both of b 1 symmetry in the case of the C 2v point group). [4,5] Thus the electronic properties of M(CO) 4 (diimine) make their use quite essential in areas such as the investigation of polymerization processes, [2] the labeling of biomolecules, [6] and the exploitation of solar energy. [7] All the structures of tetracarbonyl diimine compounds, which are either crystallographically elucidated or theoretically predicted, share two common features.…”

Section: Introductionmentioning

confidence: 99%

“…In both cases the linearity of the two CO units is no longer valid. [4][5][8][9] It is also worth mentioning that the M-C-O angle often changes upon electronic excitation.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, this procedure was successfully used in the case of a related tungsten compound. [5] Secondly, we discussed the same characteristics as they evolved through a series of bidentate N-donor ligands. In the latter case, we succeeded in extracting the structure-to-properties relation (SPR) that governs these compounds.…”

Section: Introductionmentioning

confidence: 99%

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W(CO)₄(diimine) Structure Revised – Correlating Structure to π* Back‐Bonding

Makedonas

Mitsopoulou

2006

Eur J Inorg Chem

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The bending of axial and equatorial carbonyls, one of the main structural features of the M(CO) 4 (diimine) compounds (M = Cr, Mo, and W), is elucidated in terms of the π* backbonding theory by a frontier molecular orbital analysis. Employing W(CO) 4 (phen) (phen = 1,10-phenanthroline) as a reference compound has proved that the deviation from orthogonality stabilizes the structure by a total amount of 2.95 kJ/ mol. Moreover, by an extended comparison of several W(CO) 4 (diimine) structures, the importance of the magnitude of the binding angle in determining the bonding in these complexes in comparison to the traditional approach of the W-C and C-O bond lengths is underlined. As a result, it is

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Section: Evolution Of Back-donation In W(co) 4 (Phen)mentioning

confidence: 99%

Section: Evolution Of Back-donation In W(co) 4 (Phen)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…In both cases the linearity of the two CO units is no longer valid. [4][5][8][9] It is also worth mentioning that the M-C-O angle often changes upon electronic excitation.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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W(CO)₄(diimine) Structure Revised – Correlating Structure to π* Back‐Bonding

Makedonas

Mitsopoulou

2006

Eur J Inorg Chem

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Divergent Electronic Structures of Isoelectronic Metalloclusters: Tungsten(II) Halides and Rhenium(III) Chalcogenide Halides

Gray

2009

Chemistry A European J

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Same but different: DFT calculations on hexanuclear tungsten(II) halide clusters [W(6)X(8)X'(6)](2-) (X, X'=Cl, Br, I) indicate a breakdown in the isoelectronic analogy between themselves and the isostructural rhenium(III) chalcogenide clusters [Re(6)S(8)X(6)](4-) (see figure).The hexanuclear tungsten(II) halide clusters and the sulfido-halide clusters of rhenium(III) are subsets of a broad system of 24-electron metal-metal bonded assemblies that share a common structure. Tungsten(II) halide clusters and rhenium(III) sulfide clusters luminesce from triplet excited states upon ultraviolet or visible excitation; emission from both cluster series has been extensively characterized elsewhere. Reported here are density-functional theory studies of the nine permutations of [W(6)X(8)X'(6)](2-) (X, X'=Cl, Br, I). Ground-state properties including geometries, harmonic vibrational frequencies, and orbital energy-level diagrams, have been calculated. Comparison is made to the sulfide clusters of rhenium(III), of which [Re(6)S(8)Cl(6)](4-) is representative. [W(6)X(8)X'(6)](2-) and [Re(6)S(8)Cl(6)](4-) possess disparate electronic structures owing to the greater covalency of the metal-sulfur bond and hence of the [Re(6)S(8)](2+) core. Low-lying virtual orbitals are raised in energy in [Re(6)S(8)Cl(6)](4-) with the result that the LUMO+7 (or LUMO+8 in some cases) of tungsten(II) halide clusters is the LUMO of [Re(6)S(8)Cl(6)](4-) species. An inversion of the HOMO and HOMO-1 between the two cluster series also occurs. Time-dependent density-functional calculations using asymptotically correct functionals do not recapture the experimentally observed periodic trend in [W(6)X(14)](2-) luminescence (E(em) increasing in the order [W(6)Cl(14)](2-) < [W(6)Br(14)](2-) < [W(6)I(14)](2-)), predicting instead that emission energies decrease with incorporation of the heavier halides. This circumstance is either a gross failure of the time-dependent formalism of DFT or it indicates extensive multistate emission in [W(6)X(8)X'(6)](2-) clusters. The inapplicability of isoelectronic analogies between clusters of Group 6 and Group 7 is emphasized.

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ChemInform Abstract: Metal Complexes of Quinoxaline Derivatives: Review (Part 1)

Dhanaraj

Johnson

2016

ChemInform

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An experimental and DFT computational study of a novel zerovalent tetracarbonyl tungsten complex of 2-(2′-pyridyl)quinoxaline

Cited by 29 publications

References 70 publications

W(CO)₄(diimine) Structure Revised – Correlating Structure to π* Back‐Bonding

W(CO)₄(diimine) Structure Revised – Correlating Structure to π* Back‐Bonding

Divergent Electronic Structures of Isoelectronic Metalloclusters: Tungsten(II) Halides and Rhenium(III) Chalcogenide Halides

ChemInform Abstract: Metal Complexes of Quinoxaline Derivatives: Review (Part 1)

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An experimental and DFT computational study of a novel zerovalent tetracarbonyl tungsten complex of 2-(2′-pyridyl)quinoxaline

Cited by 29 publications

References 70 publications

W(CO)4(diimine) Structure Revised – Correlating Structure to π* Back‐Bonding

W(CO)4(diimine) Structure Revised – Correlating Structure to π* Back‐Bonding

Divergent Electronic Structures of Isoelectronic Metalloclusters: Tungsten(II) Halides and Rhenium(III) Chalcogenide Halides

ChemInform Abstract: Metal Complexes of Quinoxaline Derivatives: Review (Part 1)

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W(CO)₄(diimine) Structure Revised – Correlating Structure to π* Back‐Bonding

W(CO)₄(diimine) Structure Revised – Correlating Structure to π* Back‐Bonding