Nicolay, Amelie and Ziegler, Micah S. S. and Small, David W. W. and Gruenbauer, Rebecca and Scheer, Manfred and Tilley, T. Don (2020) Isomerism and dynamic behavior of bridging phosphaalkynes bound to a dicopper complex. CHEMICAL SCIENCE, 11 (6). pp. 1607-1616. ISSN 2041-6520, 2041-6539
Full text not available from this repository. (Request a copy)Abstract
A dicopper complex featuring a symmetrically bridging nitrile ligand and supported by a binucleating naphthyridine-based ligand, [Cu-2(mu-eta(1):eta(1)-MeCN)DPFN](NTf2)(2), was treated with phosphaalkynes (RC P, isoelectronic analogues of nitriles) to yield dicopper complexes that exhibit phosphaalkynes in rare mu-eta(2):eta(2) binding coordination modes. X-ray crystallography revealed that these unusual "tilted" structures exist in two isomeric forms (R "up" vs. R "sideways"), depending on the steric profile of the phosphaalkyne's alkyl group (R = Me, Ad, or Bu-t). Only one isomer is observed in both solution and the solid state for R = Me (sideways) and Bu-t (up). With intermediate steric bulk (R = Ad), the energy difference between the two geometries is small enough that both are observed in solution, and NMR spectroscopy and computations indicate that the solid-state structure corresponds to the minor isomer observed in solution. Meanwhile, treatment of [Cu-2(mu-eta(1):eta(1)-MeCN)DPFN](NTf2)(2) with 2-butyne affords [Cu-2(mu-eta(2):eta(2)-(MeC CMe))DPFN](NTf2)(2): its similar ligand geometry demonstrates that the tilted mu-eta(2):eta(2) binding mode is not limited to phosphaalkynes but reflects a more general trend, which can be rationalized via an NBO analysis showing maximization of pi-backbonding.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | COORDINATED PHOSPHORUS-COMPOUNDS; BINUCLEAR COPPER(I) COMPLEXES; TRANSITION-METAL-COMPLEXES; STRUCTURAL-CHARACTERIZATION; COUPLING-CONSTANTS; CRYSTAL-STRUCTURE; ORGANIC-COMPOUNDS; SIMPLE ROUTE; LIGANDS; ALKYNE; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Chair Prof. Dr. Manfred Scheer |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 30 Mar 2021 10:14 |
| Last Modified: | 30 Mar 2021 10:15 |
| URI: | https://pred.uni-regensburg.de/id/eprint/45110 |
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