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

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Abstract

The donor properties of a series of tripodal mixed N-donor/carbene ligands derived through sequential alkylation of hydrotris(1,2,4-triazolyl)borate have been investigated by density functional theory (DFT) methods. The structures of complexes of the form [Mo(L)(CO)3]- were optimized (L = [HB(1,2,4-triazolyl)n(1,2,4-triazol-5-ylidene)3-n] - (n = 0-3), hydrotris(pyrazolyl)borate, hydrotris(3,5- dimethylpyrazolyl)borate and hydrotris(imidazol-2-ylidene)borate) and νCO frequencies for these complexes and partial charges of their Mo(CO)3 fragments were determined. Results show that ligand donation is highly tunable when compared to similar experimentally known ligands with a shift in the symmetric νCO stretching mode of -39 cm-1 on going from the tris(1,2,4-triazolyl)borate complexes to that of the triscarbene hydrotris(1,2,4-triazol-5-ylidene) and an increase in partial charge (distributed multipole analysis) of the Mo(CO)3 fragment from -0.23 to -0.48.

Original languageEnglish
Pages (from-to)2580-2583
Number of pages4
JournalJournal of Organometallic Chemistry
Volume696
Issue number13
DOIs
Publication statusPublished - 1 Jul 2011

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Borates
Carbon Monoxide
borates
Tuning
Ligands
tuning
ligands
fragments
L Forms
alkylation
Alkylation
carbenes
imidazoles
multipoles
Stretching
Density functional theory
density functional theory
shift

Cite this

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title = "Theoretical investigation of the scope of sequential ligand tuning using a bifunctional scorpionate tris(1,2,4-triazolyl)borate-based architecture",
abstract = "The donor properties of a series of tripodal mixed N-donor/carbene ligands derived through sequential alkylation of hydrotris(1,2,4-triazolyl)borate have been investigated by density functional theory (DFT) methods. The structures of complexes of the form [Mo(L)(CO)3]- were optimized (L = [HB(1,2,4-triazolyl)n(1,2,4-triazol-5-ylidene)3-n] - (n = 0-3), hydrotris(pyrazolyl)borate, hydrotris(3,5- dimethylpyrazolyl)borate and hydrotris(imidazol-2-ylidene)borate) and νCO frequencies for these complexes and partial charges of their Mo(CO)3 fragments were determined. Results show that ligand donation is highly tunable when compared to similar experimentally known ligands with a shift in the symmetric νCO stretching mode of -39 cm-1 on going from the tris(1,2,4-triazolyl)borate complexes to that of the triscarbene hydrotris(1,2,4-triazol-5-ylidene) and an increase in partial charge (distributed multipole analysis) of the Mo(CO)3 fragment from -0.23 to -0.48.",
keywords = "Carbene, DFT, Scorpionate ligands, Triazoles",
author = "Luke Robinson and Cooke, {David J.} and Elliott, {Paul I P}",
year = "2011",
month = "7",
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doi = "10.1016/j.jorganchem.2011.03.044",
language = "English",
volume = "696",
pages = "2580--2583",
journal = "Journal of Organometallic Chemistry",
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TY - JOUR

T1 - Theoretical investigation of the scope of sequential ligand tuning using a bifunctional scorpionate tris(1,2,4-triazolyl)borate-based architecture

AU - Robinson, Luke

AU - Cooke, David J.

AU - Elliott, Paul I P

PY - 2011/7/1

Y1 - 2011/7/1

N2 - The donor properties of a series of tripodal mixed N-donor/carbene ligands derived through sequential alkylation of hydrotris(1,2,4-triazolyl)borate have been investigated by density functional theory (DFT) methods. The structures of complexes of the form [Mo(L)(CO)3]- were optimized (L = [HB(1,2,4-triazolyl)n(1,2,4-triazol-5-ylidene)3-n] - (n = 0-3), hydrotris(pyrazolyl)borate, hydrotris(3,5- dimethylpyrazolyl)borate and hydrotris(imidazol-2-ylidene)borate) and νCO frequencies for these complexes and partial charges of their Mo(CO)3 fragments were determined. Results show that ligand donation is highly tunable when compared to similar experimentally known ligands with a shift in the symmetric νCO stretching mode of -39 cm-1 on going from the tris(1,2,4-triazolyl)borate complexes to that of the triscarbene hydrotris(1,2,4-triazol-5-ylidene) and an increase in partial charge (distributed multipole analysis) of the Mo(CO)3 fragment from -0.23 to -0.48.

AB - The donor properties of a series of tripodal mixed N-donor/carbene ligands derived through sequential alkylation of hydrotris(1,2,4-triazolyl)borate have been investigated by density functional theory (DFT) methods. The structures of complexes of the form [Mo(L)(CO)3]- were optimized (L = [HB(1,2,4-triazolyl)n(1,2,4-triazol-5-ylidene)3-n] - (n = 0-3), hydrotris(pyrazolyl)borate, hydrotris(3,5- dimethylpyrazolyl)borate and hydrotris(imidazol-2-ylidene)borate) and νCO frequencies for these complexes and partial charges of their Mo(CO)3 fragments were determined. Results show that ligand donation is highly tunable when compared to similar experimentally known ligands with a shift in the symmetric νCO stretching mode of -39 cm-1 on going from the tris(1,2,4-triazolyl)borate complexes to that of the triscarbene hydrotris(1,2,4-triazol-5-ylidene) and an increase in partial charge (distributed multipole analysis) of the Mo(CO)3 fragment from -0.23 to -0.48.

KW - Carbene

KW - DFT

KW - Scorpionate ligands

KW - Triazoles

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U2 - 10.1016/j.jorganchem.2011.03.044

DO - 10.1016/j.jorganchem.2011.03.044

M3 - Article

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