A new class of ligand derived from the reactions of bis(dialkylphosphino)amines and 9-diazofluorene: preparation, structure and reactivity
The reaction of tetra(isopropyl)diphosphazane (iPr-PNP) or tetraphenyldiphosphazane (Ph-PNP) with 9-diazofluorene (9-DAF) affords new chelating phosphazene ligands [<sub>F</sub>(NN)P(R)<sub>2</sub>NP(R)<sub>2</sub>(NHN)<sub>F</sub>] where F = fluorenylidene and R = <sup>i</sup>Pr (H[1a]) or Ph (H[1b]). H[1b] has been shown to react with ZnEt<sub>2</sub> and AlMe<sub>3</sub> giving mononuclear organometallic complexes ZnEt[1b] (4) and AlMe<sub>2</sub>[1b] (5), respectively, while the reaction with NaH generates the chelated sodium complex Na(THF)<sub>2</sub>[1b] (6). Complexes 4, 5, and 6 have been fully characterized, and the solid-state structures of all complexes in this study have been authenticated using single-crystal X-ray diffraction. Complexes 4 and 5 catalyze the ring-opening copolymerization (ROCOP) of cyclohexene oxide (CHO) and phthalic anhydride (PA) giving polyesters in the presence of bis(triphenylphosphine)iminium chloride (PPNCl) as a nucleophilic co-catalyst, yielding moderate molar masses with narrow dispersities.
Authors
- Christopher M. Kozak (ORCID: https://orcid.org/0000-0001-8205-4130)
- Jason A. C. Clyburne (ORCID: https://orcid.org/0000-0002-0722-4862)
- Katherine N. Robertson (ORCID: https://orcid.org/0000-0002-5602-8059)
- Matthew J.J. Laprade (ORCID: https://orcid.org/0000-0003-4624-6228)
Institutions
- Memorial University of Newfoundland (CA)
- Saint Mary's University (CA)
Publication Details
- Journal
- Dalton Transactions
- Published
- 2025-01-01
- DOI
- https://doi.org/10.1039/d4dt03402c
- Primary Topic
- Synthesis and characterization of novel inorganic/organometallic compounds
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Saint Mary’s University
- Canada Foundation for Innovation
- Dalhousie University
- Memorial University of Newfoundland
- Natural Sciences and Engineering Research Council of Canada