One-dimensional polymers based on silver(I) cations and organometallic cyclo-P3 ligand complexes.
The synthesis and characterization of the first supramolecular aggregates incorporating the organometallic cyclo-P3 ligand complexes [CpRMo(CO)2(eta3-P3)] (CpR=Cp (C5H5; 1a), Cp* (C5(CH3)5; 1b)) as linking units is described. The reaction of the Cp derivative 1a with AgX (X=CF3SO3, Al{OC(CF3)3}4) yields the one-dimensional (1D) coordination polymers [Ag{CpMo(CO)2(mu,eta3:eta1:eta1-P3)}2]n[Al{OC(CF3)3}4]n (2) and [Ag{CpMo(CO)2(mu,eta3:eta1:eta1-P3)}3]n[X]n (X=CF3SO3 (3a), Al{OC(CF3)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 AgCF3SO3 is used, polymer 3a is obtained regardless of reactant stoichiometry whereas in the case of Ag[Al{OC(CF3)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(CF3)3}4] to yield the 1D polymer [Ag{Cp*Mo(CO)2(mu,eta3:eta2:eta1-P3)}2]n[Al{OC(CF3)3}4]n (4), the crystal structure of which differs from that of polymer 2 in the coordination mode of the cyclo-P3 ligands: in 2, the Ag+ cations are bridged by the cyclo-P3 ligands in a eta1:eta1 (edge bridging) fashion whereas in 4, they are bridged exclusively in a eta2:eta1 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 31P NMR spectroscopy. Solid-state 31P 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.
Gregoriades
Laurence J
LJ
Institut für Anorganische Chemie der Universität Regensburg, 93040 Regensburg, Germany. gregoril@chemie.hu-berlin.de
Wegley
Brian K
BK
Sierka
Marek
M
Brunner
Eike
E
Gröger
Christian
C
Peresypkina
Eugenia V
EV
Virovets
Alexander V
AV
Zabel
Manfred
M
Scheer
Manfred
M
D002245:Carbon Dioxide / Q000737:chemistry; D002412:Cations / Q000737:chemistry; D003500:Cyclization; D008024:Ligands; D015394:Molecular Structure; D010758:Phosphorus / Q000737:chemistry; D011108:Polymers / Q000138:chemical synthesis*; D012834:Silver / Q000737:chemistry*; D014965:X-Rays
D002412:Cations; D008024:Ligands; D011108:Polymers; D002245:Carbon Dioxide; D010758:Phosphorus; D012834:Silver