New main group architectures for materials and catalysis

PN Frameworks as Building Blocks to Functional Materials.

Ligands and compounds based on carbon frameworks have had a central role in the development of modern chemistry. However, over the past three decades, in particular, there has been an increased interest in analogous arrangements based on a much broader range of main group elements that offer a rich variety of reactivity and geometry. In particular, cyclodiphosphazanes, [R’P(µ-NR)]2, comprising various R and R’ substituents have received considerable attention in the literature. However, despite having a history that backdates more than a century, the full chemical potential of the phosphazanes has not yet been unlocked, mainly due to their inherent instability. Hence, we continue our endeavour to attain a complete understanding of the pathways and mechanisms involved in their kinetic and thermodynamic stabilization.

Selected publications:

  • A Facile Modular Addition Approach to Size-Controlled Synthesis of Oxo-bridged Phosphazane Macrocycles. X. Shi, F. León, R. Ganguly, H. C. Ong, J. Díaz, and F. García.* Comm. Chem., 2021, Accepted, DOI: 10.1038/s42004-021-00455-9.
  • N-bridged Acyclic Trimeric poly-Cyclodiphosphazanes: Highly Tuneable Building Blocks within the Cyclodiphosphazane Family.  Angew. Chem., Int. Ed., 2020, 59, 22100-22108. DOI: 10.1002/anie.202008214.
  • Synthesis of Unique Phosphazane Macrocyclices via Steric Bond Activation. Inorg. Chem., 2018, 57, 10993–11004. DOI: 10.1021/acs.inorgchem.8b01596
  • Cis-cyclodiphosph(V/V)azane as Highly Stable and Robust Main Group Supramolecular Building Blocks. CrystEngComm., 2018, 20, 5998-6004. DOI:10.1039/C8CE00395E. (Invited contribution to a Thematic series:  “New Talent”)
  • Steric C-N bond activation on the dimeric macrocycle [{P(µ-NR)2(µ-NR)]2. Chem. Commun., 2015, 51, 16468 – 16471. DOI: 10.1039/C5CC06034F. CC_cover
  • Synthesis and Hydrolytic Studies on the Air-Stable [(4-CN-PhO)(E)P(µ-NtBu)]2 (E = O, S and Se) cyclodiphosphazanes.  Inor. Chem., 2015, 54, 6423 – 6432.  DOI:10.1021/acs.inorgchem.5b00735PAPER 2-GA
 
Aryl-NHC group 13 Trimethyl complexes: Synthesis, Structural Stability, and Reactivity

Employing Arduengo carbenes as highly nucleophilic bases to stabilize transition metal complexes for organic synthesis has been extensively explored over the last three decades. Conversely, in the case of N-heterocyclic group 13 trimethyl metal complexes, only a limited range of compounds have been applied during organic transformations, despite having shown excellent catalytic activity. With much yet to be explored, the synthesis, characterization, stability and reactivity of new NHC group 13 complexes is currently a flourishing area of study for main group chemists.

Selected Publications: 

  •