Journal article
Modifying Phosphorus(III) Substituents to Activate Remote Ligand-Centered Reactivity in Triaminoborane Ligands
Organometallics, Vol.39(13), pp.2526-2533
07/13/2020
DOI: 10.1021/acs.organomet.0c00321
Abstract
Triaminoborane-bridged diphosphorus ligands called TBDPhos can undergo cooperative ligand-centered reactions at the 1,8,10,9-triazaboradecalin (TBD) backbone while bound to metals, but the factors that control this reactivity are not well understood. Previous studies showed that TBDPhos reactivity is highly sensitive to phosphorus substituents, ancillary ligands, and metal coordination environment despite these changes being significantly removed from the reactive N–B bond. Here we describe how exchanging phenyl and ethyl substituents attached to phosphorus with methoxy turns on ligand-centered reactions in otherwise unreactive (TBDPhos)Pt(S2C6H4) and (TBDPhos)Mo(CO)4 complexes. The synthesis and characterization of the complexes are described alongside comparative reactivity studies using MeOH as a simple but effective test substrate. Complementary density functional theory (DFT) calculations on an expanded series of (TBDPhos)Pt(S2C6H4) complexes corroborate the experimental results and show that both size and electronic properties of the phosphorus substituents can significantly influence the Gibbs free energy of reaction at the remote ligand site. These results demonstrate how seemingly ancillary ligand modifications can levy significant control over ligand-centered reactivity in TBDPhos complexes, which may be relevant when considering the design of other chemically reactive ligands with Lewis acidic functional groups.
Details
- Title: Subtitle
- Modifying Phosphorus(III) Substituents to Activate Remote Ligand-Centered Reactivity in Triaminoborane Ligands
- Creators
- Kyounghoon Lee - Department of ChemistryJohnathan D Culpepper - Department of ChemistryRiffat Parveen - Department of ChemistryDale C Swenson - Department of ChemistryBess Vlaisavljevich - Department of ChemistryScott R Daly - Department of Chemistry
- Resource Type
- Journal article
- Publication Details
- Organometallics, Vol.39(13), pp.2526-2533
- Publisher
- American Chemical Society
- DOI
- 10.1021/acs.organomet.0c00321
- ISSN
- 0276-7333
- eISSN
- 1520-6041
- Grant note
- DOI: 10.13039/100000165, name: Division of Chemistry, award: 1650894; DOI: 10.13039/100006770, name: American Chemical Society Petroleum Research Fund, award: 55989-DNI3; DOI: 10.13039/100011411, name: University of South Dakota; DOI: 10.13039/100000001, name: National Science Foundation, award: 000390183; name: University of Iowa Center for Health Effects of Environmental Contamination
- Language
- English
- Date published
- 07/13/2020
- Academic Unit
- Chemistry
- Record Identifier
- 9984216587102771
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