Dimeric P-5-deltacyclene complexes: Variation of bridging modes and intact or partially opened P-C cage ligand structures

Keller I, Rohwer L, Heinemann FW, Höhn C, Zenneck U (2016)

Publication Status: Published

Publication Type: Journal article

Publication year: 2016

Journal

Publisher: ELSEVIER SCIENCE SA

Book Volume: 821

Pages Range: 91-99

DOI: 10.1016/j.jorganchem.2016.04.023

Abstract

Chiral P-C cage compound tetra-tert-butyl-P5-deltacyclene 7 and the coinage metal salts CuCl, CH3COOAg, and (PPh3)AuCl form binuclear complexes with the metal atoms in the bridging position. In the case of copper, a Cu2Cl2 ring connects two intact ligands 7, with tertiary P2 as the active donor center. For silver and gold, P5 of the cage becomes deprotonated and acts as a second ligand function. Two. parallel and linear P-M-P bridges result with a moderate M ... M d(10)-d(10) metallophilic interaction. In contrast to that, the Rh(I) ion of dimeric [(1,5-COD)RhCl](2) adds to 7 in an oxidative addition to the P-P bond of the smallest ring structure of 7, a diphosphirane. A partially opened cage structure results and three of the five P-atoms coordinate to Rh(III) to form a central Rh2P2 ring which links the cages. All four complexes are C-i symmetric in the solid state and form meso-diastereomers. Because of symmetry reasons, rac-diastereomers of the complexes should exist as well. Two sets of NMR spectra A and B are indeed observable for all of them which agree well with a pair of diastereomers, but no unambiguous relation between A and B on the one side and rac- and meso-diastereomers at the other side has been found. (C) 2016 Elsevier B.V. All rights reserved.

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APA:

Keller, I., Rohwer, L., Heinemann, F.W., Höhn, C., & Zenneck, U. (2016). Dimeric P-5-deltacyclene complexes: Variation of bridging modes and intact or partially opened P-C cage ligand structures. Journal of Organometallic Chemistry, 821, 91-99. https://dx.doi.org/10.1016/j.jorganchem.2016.04.023

MLA:

Keller, Irene, et al. "Dimeric P-5-deltacyclene complexes: Variation of bridging modes and intact or partially opened P-C cage ligand structures." Journal of Organometallic Chemistry 821 (2016): 91-99.

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