Structural changes upon replacing carbonyl groups with thiocarbonyl groups in first row transition metal derivatives: new insights

2012 ◽  
Vol 14 (43) ◽  
pp. 14743 ◽  
Author(s):  
R. Bruce King ◽  
Zhong Zhang ◽  
Qian-shu Li ◽  
Henry F. Schaefer, III
2013 ◽  
Vol 685 ◽  
pp. 316-323 ◽  
Author(s):  
Samira Kerouani ◽  
Tahar Sadoun ◽  
Noureddine Azzouz

Synthetic polymers are not normally biodegradable until they are degraded into low molecular mass species that can be assimilated by microorganisms. This means that biodegradation must be preceded by an abiotic degradation that produces monomeric and oligomeric products. It has been shown that carboxylic acids, alcohols, ketones, etc... can be utilized by microorganisms as nutrients to produce cell biomass. Polyethylene is resistant to oxidation and biodegradation because of the presence of antioxidants and stabilizers. However, it can be made oxo-biodegradable by the use of prooxidant additives. The most active prooxidants are those based on transition metal particulary Fe, Co and Mn. This study is an attempt to investigate the effect of prooxidant additives on the thermo-oxidation of polyethylene. Three differentes mulch films of polyethylene, two films with prooxidant additives consisting of salt based on cobalt and iron and the third film whitout prooxidant, were subjected to thermo-oxidative degradation which was conducted in an air oven at 70°C that normally occur during composting conditions, for extended time periods. Based on Fourier transform infrared spectroscopy the chemical and structural changes induced by this exposure were followed by monitoring the changes in carbonyl index and cristallinity. The results reveal an increase in the carbonyl groups with aging time more important for the polyehylene films containing a combination of Fe and Co additives than these obtained by the films with only one transition metal additive (Co) while the LDPE without additives represents no increase in carbonyl groups. The results show also a small variation of cristallinity for the two differents polyethylene films with pro-oxidant. This indicates that the transition metal prooxidant plays an important role in the degradation of PE films and accelerates the degradation of PE.


1984 ◽  
Vol 39 (9) ◽  
pp. 807-829
Author(s):  
Michael C. Böhm

The band structure of the metal-ligand-metal (M-L-M) bridged quasi one-dimensional (1D) cyclopentadienylmanganese polymer, MnCp 1, has been studied in the unoxidized state and in a partly oxidized modification with one electron removed from each second MnCp fragment. The tight-binding approach is based on a semiempirical self-consistent-field (SCF) Hartree-Fock (HF) crystal orbital (CO) model of the INDO-type (intermediate neglect of differential overlap) combined with a statistical averaging procedure which has its origin in the grand canonical ensemble. The latter approximation allows for an efficient investigation of violations of the translation symmetries in the oxidized 1D material. The oxidation process in 1 is both ligand- and metal-centered (Mn 3d-2 states). The mean-field minimum corresponds to a charge density wave (CDW) solution with inequivalent Mn sites within the employed repeat-units. The symmetry adapted solution with electronically identical 3d centers is a maximum in the variational space. The coupling of this electronic instability to geometrical deformations is also analyzed. The ligand amplitudes encountered in the hole-state wave function prevent extremely large charge separations between the 3d centers which are found in ID systems without bridging moieties (e.g. Ni(CN)2-5 chain). The symmetry reduction in oxidized 1 is compared with violations of spatial symmetries in finite transition metal derivatives and simple solids. The stabilization of the valence bond-type (VB) solution is physically rationalized (i.e. left-right correlations between the 3d centers). The computational results derived for 1 are generalized to oxidized transition metal chains with band occupancies that are simple fractions of the number of stacking units and to 1D systems that deviate from this relation. The entropy-influence for temperatures T ≠ 0 is shortly discussed (stabilization of domain or cluster structures).


1983 ◽  
Vol 38 (5) ◽  
pp. 587-591 ◽  
Author(s):  
Alexander Filippou ◽  
Ernst Otto Fischer

AbstractReaction of trans-bromotetracarbonyl(phenylcarbyne)-complexes of chromium, molybdenum and tungsten and trans-bromotetracarbonyl(methylcarbyne) complexes of chromium and tungsten with the bidentate ligands 2,2′-bipyridyl and 1,10-phenanthroline results in the replacement of two carbonyl groups leading to very thermostable carbyne complexes with the general formula Br(CO)2LMCR (L: 2,2′-bipy, ophen; M: Cr, Mo, W; R : CH3, C6H5).


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