LN-1 and LN-2 are two Ru(II) complexes coordinated to the phosphine and amines simultaneously, each with two chlorides. PPh3 is the phosphine and the amine is piperidine (LN-1) and perhydroazepine (LN-2). The two compounds are complexes five-coordinated square pyramidal geometry, with the amine in the axial plane. LN-1 and LN-2 were tested for the first time as initiator for piperine self-metathesis olefin. The system variables chosen to this study were the reactional time (24, 48 and 72 h), catalyst:substrate ratio (1:1 and 1:10 mol) and temperature (25 e 50 ºC). Results were analyzed by GC-ME. None olefin metathesis product was noted in the experiments to 25 ºC for until 72 h, in any catalyst:substrate ration. However, to 50 ºC for 72 h, olefin metathesis product from piperine was observed. LN-1 presented yield of c.a. 29% of product in the mixture and LN-2 were c.a. 39%. The product is interesting and unheard, it has two 1,3-benzildiaxine groups, interleaved for one unsaturated carbon chain. In the experiments with catalyst:substrate ratio of 1:10 mol there was no product formation. The results were discussed in function of the electronic and steric properties of the ancillary ligand of LN1 and LN-2.

Diesters of norbornene 2,3-dicarboxylic acid (NBE-(COOR)2), in which R is an alkyl group, were synthesized from one-pot synthesis method with 5-norbornene-2,3-dicarboxylic acid and methanol and ethanol. The new monomers were, respectively, the dimethyl ester NBE-(COOCH3)2 and diethyl ester NBE-(COOCH2CH3)2. Norbornene was mixed with these monomers at different proportions and copolymerized via ring-opening metathesis polymerization (ROMP) with 1st generation Grubbs' catalyst. All experiments were conducted under air atmosphere to obtain the isolated polymer. Yield results show that elongation of the R group influenced the copolymerization process. At the same co-monomer proportion, the yield decreases as a function of the R group elongation. Thermogravimetric analysis (TGA) was performed and, in all cases, more than one thermal degradation process was observed. The first process was assigned to pendent group degradation, whereas the second process was assigned to main chain degradation. These thermal processes were also influenced by different elongation of the aliphatic group of the pendent chain.

Ruthenium benzylidene complexes were evaluated as catalysts in atom-transfer radical polymerization (ATRP) of methyl methacrylate (MMA) under different reaction conditions. The mechanism by which Grubbs 1st and 2nd generation catalysts mediate olefin metathesis has been studied, little is known regarding the mechanism of ATRP reaction promoted by these complexes. Conversion and semilogarithmic kinetic plots as a function of time were correlated to the different catalysts and reaction conditions; especially in the presence of Al(OiPr)3 as additive. Molecular weight (Mn) and polydispersity index (PDI) values changed with different catalysts in the presence or absence of Al(OiPr)3. Kinetic studies by 1H NMR revealed that two complexes in the presence of Al(OiPr)3 are converted into ATRP-active with the dissociation of PCy3, but with the benzylidene group preserved. More controlled polymerizations were achieved using Grubbs 1st and, the presence of Al(OiPr)3 improved the control levels for both catalysts.

Ring Opening Metathesis Polymerization (ROMP) of cyclic olefins is a powerful transition metal-catalyzed reaction for syntheses of polymers and copolymers. The key feature of this reaction is the [2+2]-cycloaddition mechanism, with retention of the olefinic unsaturation in the polymer chain and occurrence of living polymerization. With the development of metal-carbene type catalysts for this process, many addressed polymeric materials have been successfully prepared to be employed in several fields of the science and technology. This review summarizes recent examples of syntheses of polymers with amphiphilic features such as block, graft, brush or star copolymers; as well syntheses of biomaterials, dendronized architectures, photoactive polymers, cross-linked or self-healing materials, and polymers from renewed supplies.