Simultaneous End-On/Side-On Coordination Modes of a Diphosphorus Tetrahedral Complex Imposed by Pre-organization of Oligometallic Cu-I Acceptors

Welsch, Stefan and Lescop, Christophe and Balazs, Gabor and Reau, Regis and Scheer, Manfred (2011) Simultaneous End-On/Side-On Coordination Modes of a Diphosphorus Tetrahedral Complex Imposed by Pre-organization of Oligometallic Cu-I Acceptors. CHEMISTRY-A EUROPEAN JOURNAL, 17 (33). pp. 9130-9141. ISSN 0947-6539,

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Abstract

The reaction of the [{CpMo-(CO)(2)}(2)(mu,eta(2):eta(2)-P-2)] (Cp=cyclopentadienyl) metallo-ligand 2 with pre-organized Cu-I bi- and trimetallic precursors afforded new coordination complexes with unprecedented coordination modes for a Mo2P2 complex. Variable-temperature solution and solid-state P-31 NMR spectroscopy measurements were performed and Xray diffraction studies revealed an eta(2):eta(1) coordination mode for the Mo2P2 unit of 2 in the Cu-I bimetallic complexes 3 and 4. DFT calculations were carried out to highlight the bonding situation of this unprecedented coordination mode in the CuI bimetallic compound 3. It is built up from a side-on coordination of the P-P sigma bond to one copper ion and from the interaction of the lone pair of one phosphorus atom with the second copper ion. The remaining available lone pair of the second phosphorus atom can be involved as well to interact with an additional metal centre, as evidenced in the Cu-I trimetallic compound 5 in which an eta(2):eta(1):eta(1) coordination mode of the ligand 2 is observed. Derivative 3 can be used as a molecular clip to obtain discrete pi-stacked dimers through a ligand exchange reaction between acetonitrile ligands and cyano-capped pi-conjugated systems, indicating the stability of the new eta(2):eta(1) coordination mode.

Item Type: Article
Uncontrolled Keywords: ONE-DIMENSIONAL POLYMERS; TRANSITION-METAL-COMPLEXES; LIGAND COMPLEXES; ELECTRONIC-STRUCTURE; BRIDGING PHOSPHANES; CONJUGATED SYSTEMS; NMR-SPECTROSCOPY; P-4 ACTIVATION; BASIS-SETS; PHOSPHORUS; coordination modes; copper; molybdenum; P ligands; supramolecular chemistry
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: 02 Jun 2020 10:43
Last Modified: 02 Jun 2020 10:43
URI: https://pred.uni-regensburg.de/id/eprint/20422

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