Sterically Crowded peri‐Substituted Naphthalene Phosphines and their P^V Derivatives

Abstract

X-ray crystallographic files for 1, 2, nO, nS, nSe (n= 1-3).Keywords: naphthalene, peri-substitution, intramolecular, chalcogen, phosphorus, X-Ray Structure, oxidation, DFT INDEX ENTRYSteric crowding whilst giving quasi linear E…P-C fragments does not result in 3c-4e bonds but calculations suggest these molecules are ideal precursors for radicals.

Peri-Substituted Phosphorus–Tellurium Systems–An Experimental and Theoretical Investigation of the P···Te through-Space Interaction

“…Te) 33 [Hz] figures for a significant three-centre four-electron bond (3c-4e) were reported to be around 0.55 (for 1,6-Dibromo-2-phenyl-1,2-diselenaacenaphthylene with d(Se-Se) = 2.516 and 2.542 Å). 15,36 However, weak three-centre four-electron type interactions were discussed for compounds with a WBI of around 0.14 to 0.19 (e.g. PhTe-Acenap-TePh, radical cations of PhSe-Nap-P(E)Ph 2 (E = O, S, Se)).…”

“…This was also observed in the peri-substituted phosphorus-selenium systems Ph 2 (E)P-Nap-SePh (E = O, S, Se)). 15,32 21…”

Bridging the Gap: Attractive 3c–4e Interactions in peri‐Substituted Acenaphthylenes

“…[12,13] When electron density is delocalized over formally nonbonded atoms, the degree to which the delocalization contributes to the bonding between these atoms is of particular interest. [8,[14][15][16][17][18][19] Heavier third and fourth row peri-substituents, susceptible to hypervalent bonding, can be forced to interact well within the sum of van der Waals radii. However, the nature, size and number of the substituents attached to the peri-atoms and the makeup of the rigid backbone can have a notable affect on the formally non-bonded peri-separations.…”

Silver(i) coordination complexes and extended networks assembled from S, Se, Te substituted acenaphthenes

“…As such, the metal-ligand interaction is 30 an important building block for the design and manufacture of organic solids and metal-organic frameworks (MOFs). [4][5][6] Control over the polymeric architecture of the network is, nevertheless a major challenge, governed as it is by additional 35 experimental factors such as the oxidation state of the metal, the coordination geometry, the metal-to-ligand ratio, the nature and spacer length of the bridging ligand, the presence of solvent molecules and the nature of the counter-anions. 4,7 Subtle modification to any of these parameters can significantly alter the 40 structure of the complexes produced, generating for example classical monomeric, mononuclear species, linear chain polymers or extended three-dimensional networks.…”

“…[1][2][3][4][5][6] The archetypical design utilises bridging organic ligands as ridgid supports to link central 25 metal ions in an ordered lattice, creating extended, multidimensional networks. [4][5][6] Functionalisation of the ligand shell allows the properties, topology and geometry of the extended network to be tailored, allowing new functional materials to be developed. As such, the metal-ligand interaction is 30 an important building block for the design and manufacture of organic solids and metal-organic frameworks (MOFs).…”