The role of neutral Rh(PONOP)H, free NMe2H, boronium and ammonium salts in the dehydrocoupling of dimethylamine-borane using the cationic pincer [Rh(PONOP)(η2-H2)]+ catalyst

The σ-amine-borane pincer complex [Rh(PONOP)(η1-H3B·NMe3)][BArF4] [2, PONOP = κ3-NC5H3-2,6-(OPtBu2)2] is prepared by addition of H3B·NMe3 to the dihydrogen precursor [Rh(PONOP)(η2-H2)][BArF4], 1. In a similar way the related H3B·NMe2H complex [Rh(PONOP)(η1-H3B·NMe2H)][BArF4], 3, can be made in situ, but this undergoes dehydrocoupling to reform 1 and give the aminoborane dimer [H2BNMe2]2. NMR studies on this system reveal an intermediate neutral hydride forms, Rh(PONOP)H, 4, that has been prepared independently. 1 is a competent catalyst (2 mol%, ∼30 min) for the dehydrocoupling of H3B·Me2H. Kinetic, mechanistic and computational studies point to the role of NMe2H in both forming the neutral hydride, via deprotonation of a σ-amine-borane complex and formation of aminoborane, and closing the catalytic cycle by reprotonation of the hydride by the thus-formed dimethyl ammonium [NMe2H2]+. Competitive processes involving the generation of boronium [H2B(NMe2H)2]+ are also discussed, but shown to be higher in energy. Off-cycle adducts between [NMe2H2]+ or [H2B(NMe2H)2]+ and amine-boranes are also discussed that act to modify the kinetics of dehydrocoupling

Densidade de substratos dependendo dos métodos de análise e níveis de umidade Density of substrates depending on the analytical methods and the levels of humidity

O termo "substrato para plantas" refere-se ao meio de crescimento usado no cultivo em recipientes, freqüentemente resultante da mistura de materiais. A qualidade final depende das propriedades físicas e químicas de cada componente e da interação entre eles, as quais precisam ser caracterizadas. Apesar de obras referenciais serem unânimes em incluir a densidade volumétrica na caracterização de substratos, ocorrem dificuldades para interpretar laudos emitidos por diferentes laboratórios, porque estes utilizam métodos diferentes ou variações de um mesmo método. Além das diferenças entre os métodos, podem ocorrer outras causas de variação na obtenção dos resultados de uma mesma amostra. O presente trabalho visa demonstrar duas das causas de variação na determinação da densidade volumétrica: 1) o método de análise [método do duplo anel (CEN), método utilizado pela indústria (IND) e método da autocompactação (AUTO)] dos substratos pó de coco, areia de rio média lavada, turfa fibrosa in natura e Plantmax® Hortaliça; 2) e o nível inicial de umidade (0,62, 0,69 e 0,72g/g) em amostras de turfa fibrosa in natura. Constatou-se que os valores de densidade, determinados pelo método AUTO, representam cerca de 20% a mais do que os valores determinados pelo método IND; as relações entre os métodos AUTO e CEN, bem como CEN e IND não são uniformes, variando conforme o material; a umidade inicial da amostra também representa causa de variação nos resultados.<br>The term "substrate for plants" refers to the growth medium used in cultivation in containers, often resulting from the mixture of materials. The final quality depends on the physical and chemical attributes of each component and the interaction among them, which need to be characterized. Although the reference works are unanimous including volumetric density for substrate characterization, the interpretation of reports from different laboratories is difficult, because they use different methods or variations of the same method. In addition to the differences between methods, there might be other causes of variation in the achievement of results from a single sample. This work aims to demonstrate two of the causes of variation in the determination of density by volume: 1) the method of analysis [method of double ring (CEN), the method used by the industry (IND) and method of auto compact (AUTO) of substrate dust] of coconut, washed sand of river, peat brown in natura and Plantmax® for horticulture; 2) and the initial level of humidity (0.62, 0.69 and 0.72 g/g) in in natura samples of peat brown. The density values, determined by the AUTO, represented about 20% more than the values determined by IND; relations between the AUTO and CEN methods as well as CEN and IND were not uniform, depending on the material. Initial moisture of the sample also represents the cause of variation in the results