Complexes in polymers: FT‐IR spectra and photochemistry of some monomeric organometallic carbonyl complexes in polystyrene, poly(methyl methacrylate), polystyrene—poly(methyl methacrylate) and polystyrene—polyacrylonitrile copolymers

1988

The infrared spectra of [CpFe(CO)2]2, [CpMo(CO)3]2 and Mn2(CO)10 (Cp=η‐C5H5) embedded in films of polystyrene (PS), poly(methyl methacrylate) (PMMA), and polystyrene‐polyacrylonitrile (PSAN), are comparable with those of the dimers in toluene, ethyl acetate and acetonitrile, respectively. Irradiation of the embedded dimers with UV light led to decomposition in PS and PMMA, while in PSAN the complexes Cp2Fe2(CO)3PSAN and Mn2(CO)9PSAN were formed, wherein a pendant nitrile group is coordinated to one of the metal atoms. Exposure of the embedded dimers to iodine vapour gave CpFe(CO)2I, CpMo(CO)3I and Mn(CO)5I with the reaction being much slower in PMMA than in PS.

Complexes in polymers II: FT‐IR spectra, iodine oxidation, and photochemistry of [(η⁵‐C₅H)Fe(CO)₂]₂, [(η⁵‐C₅H₅)Mo(CO)₃]₂ and Mn₂(CO)₁₀ in polystyrene, poly(methyl methacrylate) and polystyrene–polyacrylonitrile copolymer

Shaver

1988

Complexes in polymers III: Addition reactions of trans‐Ir(PPh₃)₂(CO)Cl embedded in polystyrene with hydrogen, oxygen, sulfur dioxide, carbon monoxide and gaseous iodine and of (η‐C₅H₅)Ru(η⁴‐1,5‐cyclooctadiene)Cl in polystyrene with carbon monoxide

Shaver

1989

The addition reactions of tran~-Ir(PPh~)~(CO)Cl embedded in films of polystyrene (PS) with hydrogen, oxygen, sulfur dioxide, carbon monoxide and gaseous iodine were monitored by infrared spectroscopy and found to be similar to those occurring in toluene. While the reaction with iodine was rapid at the surface of the film as determined by attenuated-total-reflectance infrared spectroscopy, the reaction was much slower in the body of the film, as shown by transmission infrared spectroscopy. No such difference was observed for oxygen. The complex CpRu(C0D)Cl (Cp = T C~H~, COD = 1,5-cyclooctadiene) in PS readily undergoes ligand substitution by carbon monoxide (CO and 13CO) to give CpRu(C0)2Cl and C~R U ( '~C O )~C I embedded in PS, respectively.

Complexes in polymers IV. FTIR microscopic characterization of thin organic polymer films containing embedded transition‐metal carbonyl complexes

Markwell

et al. 1992

Self Cite

Thin films of polystyrene (PS), poly(methy1 methacrylate) (PMMA) and polystyrene-polyacrylonitrile copolymer (PS-AN), containing various embedded transition-metal complexes, have been studied by FTIR microscopy. The spatial distributions of the transition-metal carbonyl complexes throughout the thin organic polymer films have been determined by a two-dimensional IR mapping procedure. The spectral variations observed in the distribution of the metal carbonyls throughout the different polymer films are discussed. The IR data show that the technique used to prepare the organometallic-embedded thin films (viz. freeze-drying of solutions followed by hot mechanical pressing of the residues) does in general lead to homogeneous films which may eventually find industrial application, e.g. as membrane sensors for small molecules.