New Phosphonite Ligands with High Steric Demand and Low Basicity: Synthesis, Structural Properties and Cyclometalated Complexes of Pt(II)
Abstract
:1. Introduction
2. Results
2.1. Synthesis and Properties of Terphenyl Phosphonites
- The highest TCA value among the phosphine series is 212.4°, for PArDtbp2(c-C5H9)2, in which the flanking rings of the terphenyl moiety are functionalized with two bulky tert-butyl groups at the meta positions and two cyclopentyl groups are bound to the P atom;
- The TCA values for PArXyl2R2 phosphines, which bear the same terphenyl group as the phosphonites of this work, are in the range 153.9–187.3, with the highest value for the highly steric demanding R = cyclohexyl;
- PArXyl2(OPhNO2)2 and PArXyl2(OPhNO2,Me)2 have TCA values of 218.1 and 226.5, respectively, i.e., significantly higher than those of the related PR2ArXyl2;
- The TCA increases by ca. 60° from the dimethyl terphenyl phosphine PArXyl2Me2 to the dimethoxy phosphonite PArXyl2(OMe)2;
- Data reported for a series of PR3 and P(OR)3 ligands indicate that, in most cases, the TCA is reduced slighlty when passing from a phosphane to the related phosphite, e.g., from PPh3 (TCAtetrehedral = 165.8°) to P(OPh)3 (TCAtetrehedral = 152.9°).
2.2. Synthesis and Characterization of Cyclometalated Complexes of Pt(II) with PArXyl2(OPhNO2)2 and PArXyl2(OPhNO2,Me)2
- The four methyl groups of the xylyl rings give rise to one singlet at 2.10 ppm and one singlet at 21.5 ppm in the 1H and 13C{1H} NMR spectra, respectively, in accordance with fast rotation around the P—C bond on the NMR time-scale, as in the free phosphonite ligands;
- The two metalated OPhNO2,Me fragments are equivalent, as shown by the presence of only one resonance for the CH3 groups in both the 1H- and 13C{1H} NMR spectra;
- In the 1H NMR spectrum, the four diasterotopic methylene protons are coupled with the 31P nucleus, thus constituting first-order AMX spin systems, which give rise to a doublet (2JHH = 11.5 Hz, 3JHP ≈ 0 Hz) and a triplet (2JHH ≈ 3JHP = 11.5 Hz), both with 195Pt satellites;
- The six protons of the coordinated dimethylsulfide resonate as a doublet at 2.34 ppm with 4JHP = 4.0 Hz and 3JHPt = 36.4 Hz.
3. Materials and Methods
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Alcaide, M.M.; Pugliesi, M.; Álvarez, E.; López-Serrano, J.; Peloso, R. New Phosphonite Ligands with High Steric Demand and Low Basicity: Synthesis, Structural Properties and Cyclometalated Complexes of Pt(II). Inorganics 2022, 10, 109. https://doi.org/10.3390/inorganics10080109
Alcaide MM, Pugliesi M, Álvarez E, López-Serrano J, Peloso R. New Phosphonite Ligands with High Steric Demand and Low Basicity: Synthesis, Structural Properties and Cyclometalated Complexes of Pt(II). Inorganics. 2022; 10(8):109. https://doi.org/10.3390/inorganics10080109
Chicago/Turabian StyleAlcaide, María M., Matteo Pugliesi, Eleuterio Álvarez, Joaquín López-Serrano, and Riccardo Peloso. 2022. "New Phosphonite Ligands with High Steric Demand and Low Basicity: Synthesis, Structural Properties and Cyclometalated Complexes of Pt(II)" Inorganics 10, no. 8: 109. https://doi.org/10.3390/inorganics10080109