Synthesis and Characterization of Readily Modified Poly(aryl)(alkoxy)stannanes by use of Hypercoordinated Sn Monomers

• Published in: Chemistry : a European journal 2018-12, Vol.24 (70), p.18762-18771
• Main Authors: Pau, Jeffrey, D'Amaral, Gloria M., Lough, Alan J., Wylie, R. Stephen, Foucher, Daniel A.
• Format: Article
• Language: English
• Subjects: Aromatic compounds; Calorimetry; Chemical synthesis; Chemistry; Crystal structure; Crystallinity; Design modifications; Differential scanning calorimetry; Dihydrides; hypercoordination; Intermediates; Moisture; Molecular weight; Monomers; NMR; Nuclear magnetic resonance; polymerization; Polymers; polystannanes; Tin; Tin compounds
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201804145

The synthesis and solid‐state molecular structures of two dichlorido(aryl)(alkyl) tin compounds, 5 and 8, both key intermediates to tunable polystannane architectures, are reported. The materials were further investigated by single‐crystal XRD and a DFT analysis of their preferential “open and closed” geometries. Conversion of said compounds to their dihydride analogues was undertaken, followed by their application as monomers for polystannane polymer synthesis. The properties of two asymmetrical polystannanes prepared by transition‐metal‐catalyzed dehydropolymerization of dihydrido(aryl)alkylstannanes (6 and 9) were investigated. The first product was the structurally simple, modest molecular weight, semi‐crystalline light‐ and moisture‐stable polystannane 10 with NMR (119Sn) evidence of prominent Sn←O hypercoordination along the polymer backbone. The second was the lower molecular weight, tosylated four‐coordinate polystannane 11 with no evidence of hypercoordination. Differential scanning calorimetry (DSC) of polymer 10 revealed a reversible semi‐crystalline nature, whereas an amorphous character was detected for polymer 11. Polystannane 10 was also found to be exceptionally stable to both moisture and light (>6 months) and a promising candidate for the design of readily modified (i.e., tunable) polystannane materials. Building polystannanes: A simple light‐ and moisture‐stable semi‐crystalline hypercoordinated polystannane is revealed: A key design feature for asymmetrical polystannanes is the use of strongly dative‐bonded ligands that render the majority of tin(IV) centers of this main‐group inorganic polymer pentacoordinate, electron rich and protected from nucleophilic attack.