Theoretical investigation of the scope of sequential ligand tuning using a bifunctional scorpionate tris(1,2,4-triazolyl)borate-based architecture

Robinson, L. R.; Cooke, David J.; Elliott, Paul I. P.

doi:10.1016/j.jorganchem.2011.03.044

Cited by 3 publications

(3 citation statements)

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“…Cu(I) and Mo(0), respectively, represent the first and the second row transition metals, both of which are of special importance in bioinorganic chemical processes. 29,32 Furthermore, choosing both charged and neutral metal centres, the dependency of ligand tunability on charge can be obtained. In the complexes, Cu(I) is tetrahedral and Mo(0) is octahedral.…”

Section: A Model To Evaluate the Ligand Tunabilitymentioning

confidence: 99%

“…The tunabilities of tris(azolyl)borate ligands are higher (B50 cm À1 for the Cu-complexes and B53 cm À1 for the Mo-complexes), which are also considerably higher than the symmetric n CO shift of the tris(1,2,4-triazolyl)borate family substituted with one to three imidazol-2-ylidene carbenes. 32 Though the n CO data for the tetrakis(azolyl)borate ligands are not complete (due to the high computational costs), the tunabilities of the two complex groups of B54 and B62 cm À1 , respectively, are the highest. For borate ligands with the same number of azolyl substitutions, the pyrazolyl borates exhibit the smallest n CO and the tetrazolyl borates exhibit the largest, which imply that the metal to ligand back (M -CO) p-donation is the strongest in the pyrazolyl borate complexes and the weakest in the tetrazolyl borate complexes, in line with the trend of the higher N content in the ring corresponding to its weaker electron donating capability.…”

Section: Ligand Tunabilitymentioning

confidence: 99%

“…[29][30][31] In addition, Elliott's group has theoretically studied CO vibrations in a series of [Mo(0)(borate)(CO) 3 ] À complexes, with the tripodal borate ligands composed of mixed azolyl groups (including pyrazolyl and 1,2,4-triazolyl groups) and structurally close related carbenes. 32 The carbene-azolyl mixed borate ligands are found to be able to tune the electronic structure of the metal substantially. However, a full-scale survey of the tunability of the poly(azolyl)borate ligand family is still lacking.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical survey of the ligand tunability of poly(azolyl)borates

Tang

2015

Phys. Chem. Chem. Phys.

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Using density functional calculations, we have systematically investigated a series of homoleptic poly(azolyl)borate ligands, which display unusual steadily declining bond strengths accompanied by bond contractions when the azolyl groups are sequentially substituted to the parent BH4(-). As ligands, their effects on the coordinated metal ions (Cu(i) and Mo(0)) are quantitatively represented by two ligand tunability descriptors: the vibration frequency (νCO) of the CO groups complexed to the metal ions and the charge of the metal-(CO)x moiety, between which a good linear correlation exists. For the same number of azolyl substitutions, the boundary of ligand tunability is always marked by the pyrazolyl and tetrazolyl groups at the two ends, which feature the lowest and the highest nitrogen content in the azolyl ring, respectively. With the increase of the azolyl substitution number in the borate ligands, the νCO range expands, indicating a higher tunability of the ligands. The type of metal ion and the charge they carry play minor roles in influencing the ligand tunability.

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Section: A Model To Evaluate the Ligand Tunabilitymentioning

confidence: 99%

Section: Ligand Tunabilitymentioning

confidence: 99%