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One‐Dimensional Polymers Based on Silver(I) Cations and Organometallic cyclo ‐P 3 Ligand Complexes
Author(s) -
Gregoriades Laurence J.,
Wegley Brian K.,
Sierka Marek,
Brunner Eike,
Gröger Christian,
Peresypkina Eugenia V.,
Virovets Alexander V.,
Zabel Manfred,
Scheer Manfred
Publication year - 2009
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.200900309
Subject(s) - homoleptic , chemistry , stoichiometry , ligand (biochemistry) , crystallography , polymer , crystal structure , supramolecular chemistry , derivative (finance) , yield (engineering) , organometallic chemistry , stereochemistry , metal , organic chemistry , materials science , biochemistry , receptor , financial economics , economics , metallurgy
The synthesis and characterization of the first supramolecular aggregates incorporating the organometallic cyclo ‐P 3 ligand complexes [Cp R Mo(CO) 2 (η 3 ‐P 3 )] (Cp R =Cp (C 5 H 5 ; 1a ), Cp* (C 5 (CH 3 ) 5 ; 1b )) as linking units is described. The reaction of the Cp derivative 1a with AgX (X=CF 3 SO 3 , Al{OC(CF 3 ) 3 } 4 ) yields the one‐dimensional (1D) coordination polymers [Ag{CpMo(CO) 2 (μ,η 3 :η 1 :η 1 ‐P 3 )} 2 ] n [Al{OC(CF 3 ) 3 } 4 ] n ( 2 ) and [Ag{CpMo(CO) 2 (μ,η 3 :η 1 :η 1 ‐P 3 )} 3 ] n [X] n (X=CF 3 SO 3 ( 3a ), Al{OC(CF 3 ) 3 } 4 ( 3b )). The solid‐state structures of these polymers were revealed by X‐ray crystallography and shown to comprise polycationic chains well‐separated from the weakly coordinating anions. If AgCF 3 SO 3 is used, polymer 3a is obtained regardless of reactant stoichiometry whereas in the case of Ag[Al{OC(CF 3 ) 3 } 4 ], reactant stoichiometry plays a decisive role in determining the structure and composition of the resulting product. Moreover, polymers 3a, b are the first examples of homoleptic silver complexes in which Ag I centers are found octahedrally coordinated to six phosphorus atoms. The Cp* derivative 1b reacts with Ag[Al{OC(CF 3 ) 3 } 4 ] to yield the 1D polymer [Ag{Cp*Mo(CO) 2 (μ,η 3 :η 2 :η 1 ‐P 3 )} 2 ] n [Al{OC(CF 3 ) 3 } 4 ] n ( 4 ), the crystal structure of which differs from that of polymer 2 in the coordination mode of the cyclo ‐P 3 ligands: in 2 , the Ag + cations are bridged by the cyclo ‐P 3 ligands in a η 1 :η 1 (edge bridging) fashion whereas in 4 , they are bridged exclusively in a η 2 :η 1 mode (face bridging). Thus, one third of the phosphorus atoms in 2 are not coordinated to silver while in 4 , all phosphorus atoms are engaged in coordination with silver. Comprehensive spectroscopic and analytical measurements revealed that the polymers 2 , 3a , b , and 4 depolymerize extensively upon dissolution and display dynamic behavior in solution, as evidenced in particular by variable temperature 31 P NMR spectroscopy. Solid‐state 31 P magic angle spinning (MAS) NMR measurements, performed on the polymers 2 , 3b , and 4 , demonstrated that the polymers 2 and 3b also display dynamic behavior in the solid state at room temperature. The X‐ray crystallographic characterisation of 1b is also reported.