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Simultaneous End‐On/Side‐On Coordination Modes of a Diphosphorus Tetrahedral Complex Imposed by Pre‐organization of Oligometallic Cu I Acceptors
Author(s) -
Welsch Stefan,
Lescop Christophe,
Balazs Gabor,
Réau Régis,
Scheer Manfred
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201100845
Subject(s) - bimetallic strip , chemistry , ligand (biochemistry) , crystallography , coordination complex , lone pair , coordination number , acetonitrile , coordination sphere , copper , cyclopentadienyl complex , crystal structure , metal , inorganic chemistry , ion , molecule , organic chemistry , catalysis , biochemistry , receptor
The reaction of the [{CpMo(CO) 2 } 2 (μ,η 2 :η 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 Mo 2 P 2 complex. Variable‐temperature solution and solid‐state 31 P NMR spectroscopy measurements were performed and X‐ray diffraction studies revealed an η 2 :η 1 coordination mode for the Mo 2 P 2 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 Cu I bimetallic compound 3 . It is built up from a side‐on coordination of the PP σ 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 η 2 :η 1 :η 1 coordination mode of the ligand 2 is observed. Derivative 3 can be used as a molecular clip to obtain discrete π‐stacked dimers through a ligand exchange reaction between acetonitrile ligands and cyano‐capped π‐conjugated systems, indicating the stability of the new η 2 :η 1 coordination mode.