Relaxed but highly compact diansa metallacyclophanes
Farràs, Pau Teixidor, Francesc Rojo, Isabel Kivekäs, Raikko Sillanpää, Reijo González-Cardoso, Paul V. Viñas, Clara
Farràs, Pau
Teixidor, Francesc
Rojo, Isabel
Kivekäs, Raikko
Sillanpää, Reijo
González-Cardoso, Paul V.
Viñas, Clara
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Publication Date
2011-09-09
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Article
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Farràs, Pau, Teixidor, Francesc, Rojo, Isabel, Kivekäs, Raikko, Sillanpää, Reijo, González-Cardoso, Patricia, & Viñas, Clara. (2011). Relaxed but Highly Compact Diansa Metallacyclophanes. Journal of the American Chemical Society, 133(41), 16537-16552. doi: 10.1021/ja205850p
Abstract
A series of monoansa [μ-1,1′-PR-3,3′-Co(1,2-C2B9H10)2]− and diansa [8,8′-μ-(1″,2″-benzene)-μ-1,1′-PR-3,3′-Co(1,2-C2B9H9)2]− (R = Ph, tBu) cobaltabisdicarbollidephanes have been synthesized, characterized and studied by NMR, MALDI-TOF-MS, UV-visible spectroscopy, cyclic voltammetry, and DFT calculations. Single crystal X-ray diffraction revealed a highly relaxed structure characterized by the title angle α of 3.8° ([7]−), this being the smallest angle α for a metallacyclophane. In such compounds, the metal-to-phosphorus distance is less than the sum of their van der Waals radii. The availability of a phosphorus lone pair causes an electron delocalization through the metal, as shown by the abnormal 31P NMR chemical shift. Remarkably, the combination of a phosphine donor and a phenyl acceptor moieties causes a synergistic effect that is observed through the different techniques used in this study. The importance of having an available lone pair is demonstrated by the oxidation of phosphorus with hydrogen peroxide, sulfur, and elemental black selenium to produce the corresponding PV compounds. When the electron lone pair is used to form the bond with the corresponding chalcogen atom, the communication between the donor and acceptor moieties on the diansa metallacyclophane is shut down.
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Publisher
American Chemical Society
Publisher DOI
10.1021/ja205850p
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Attribution-NonCommercial-NoDerivs 3.0 Ireland