Heteroleptic Organostannylenes and an Organoplumbylene Bearing Phosphorus‐Containing Pincer‐Type Ligands – Structural Variations and Insights into the Configurational Stability

Abstract

AbstractThe syntheses of the arylphosphonic esters 3‐Br‐5‐tBu‐1‐{P(O)(OiPr)2}C6H3 (1), 5‐tBu‐1,3‐{P(O)(OiPr)2}2C6H3 (2), of the heteroleptic intramolecularly coordinated organostannylenes [4‐tBu‐2,6‐{P(O)(OiPr)2}2C6H2]SnX (3, X = Cl; 4, X = Br; 5, X = I; 6, X = SPh), the organoplumbylene [4‐tBu‐2,6‐{P(O)(OiPr)2}2C6H2]PbCl (7), and the transition metal complex [4‐tBu‐2,6‐{P(O)(OiPr)2}2C6H2]Sn(Cl)Cr(CO)5 (8) are reported. The compounds were characterized by 1H, 13C, 31P, 31P MAS (3), 119Sn, and 119Sn MAS (3) NMR spectroscopy, electrospray ionization mass spectrometry (3), Mössbauer spectroscopy (3–5, 8) and single‐crystal X‐ray diffraction analyses (2, 3–5, 6–8). In contrast to its ethoxy‐substituted analogue [4‐tBu‐2,6‐{P(O)(OEt)2}2C6H2]SnCl, compound 3, like the thiophenolate derivative 6, is monomeric in solution as well as in the solid state. This difference is also manifested by the Mössbauer as well as solid state NMR spectroscopic data. On the other hand, the corresponding organoplumbylene 7 shows a similar chlorido‐bridged polymeric structure as its ethoxy‐substituted analogue. Variable‐temperature and concentration‐dependent 1H and 31P NMR spectra reveal, on the respective time scales, the tin atom in compound 3 to be configurationally unstable and those in compounds 6 and 8 to be configurationally stable. DFT calculations support a chlorido‐bridged dimer to account for the configurational instability in compound 3. Surprisingly and in contrast to compounds 3 and 6, the organobromido‐ and organoiodidostannylenes 4 and 5, respectively, show intermolecular Sn···Sn distances of 3.6809(4) and 3.5953(4) Å being shorter than twice the van der Waals radius of tin (2.20 Å). Quantum chemical calculations were performed on monomeric and dimeric model compounds, which revealed a weak Sn···Sn bonding interaction for dimer 3 (16 kJ·mol–1) as well as for dimer 5 (20 kJ·mol–1) whereas the hypothetical model compound p‐tBuC6H4SnI showed an iodido‐bridged dimer rather than a Sn···Sn bonding interaction.