We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
Peri-Interactions in 8-Diphenylphosphino-1-bromonaphthalene, 6-Diphenylphosphino-5-bromoacenaphthene, and Derivatives.
- Authors
Beckmann, Jens; Do, Truong Giang; Grabowsky, Simon; Hupf, Emanuel; Lork, Enno; Mebs, Stefan
- Abstract
The syntheses and full characterizations of the peri-substituted naphthalenes (Nap) and acenaphthenes (Ace) 1-Br-8-(Ph2P)-Nap ( 1a) and 5-Br-6-(Ph2P)-Ace ( 1b), as well as their derivatives 1-Br-8-[Ph2P( E)]-Nap [ E = CH3+ (counterion I-) ( 2a); E = O ( 3a); E = S ( 4a); E = Se ( 5a)] and 5-Br-6-[Ph2P(E)]-Ace [ E = CH3+ (counterion I-) ( 2b); E = O ( 3b); E = S ( 4b); E = Se ( 5b)] are reported. In order to quantify the energetic and electronic effects of the peri-interactions, an additional set of molecules, 1c- 5c, with the bromine atom and the Ph2P( E) fragment on opposite sides of the naphthalene group was generated, which serves as reference because 1c- 5c exhibit negligible peri-interactions. The molecular arrangements of all 15 compounds were optimized at the B3PW91/6-311+G(2df, p) level of theory. The analysis of the peri-interactions was not only based on the inspection of the molecular arrangement and energies alone, but extended to a set of real-space bonding indicators (RSBI). These indicators were derived from theoretically calculated electron densities and pair densities, respectively. Particularly, the stockholder, Atoms-In-Molecules (AIM) and Electron-Localizability-Indicator (ELI-D) space partitioning schemes were used to produce Hirshfeld surfaces (HS), bond topological properties and basins of localized bonding and nonbonding electron pairs. Since 1c- 5c are 35-58 kJ ·mol-1 lower in energy than their counterparts 1a- 5a, the hypothesis of a mainly repulsive peri-interaction in 1a/b- 5a/b was confirmed. The shapes and contact patterns of the HSs of atoms and fragments involved in the peri-interactions (Br, P, E = CH3+, O, S, Se) reveal that only in 1a and 1b are peri-interactions exhibited between the bromine and the phosphorus atoms. In all other cases ( 2a/b- 5a/b), the interaction mainly occurs between the bromine atom and the E atom/fragment. According to the bond topological properties and the electron populations within the (non)bonding ELI-D basins, which both are almost unaffected by the Br-P/E peri-interaction, sterical interactions are characterized essentially by geometrical and energetical changes.
- Subjects
NAPHTHALENE derivatives; NAPHTHALENESULFONIC acids; BROMINE; HYDROGEN bonding; MOLECULAR association; ELECTRONS
- Publication
Zeitschrift für Anorganische und Allgemeine Chemie, 2013, Vol 639, Issue 12/13, p2233
- ISSN
0044-2313
- Publication type
Article
- DOI
10.1002/zaac.201300272