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Phosphasalen group IV metal complexes: synthesis, characterization and ring opening polymerization of lactide.

2020

International audience; We report the synthesis of a series of Zr and Ti complexes bearing phosphasalen which differs from salen by the incorporation of two P atoms in the ligand backbone. The reaction of phosphasalen proligands (1a-1c)H2 with Zr(CH2Ph)4 led to different products depending on the nature of the N,N-linker in the ligand. In case of ethylene-linked phosphasalen, octahedral Zr complex 2a formed as a single stereoisomer in trans geometry. With the phenylene linker, it was shown by dynamic NMR spectroscopy that complex 2b exists as a mixture of trans and cis-β isomers in solution, both enantiomers (Δ and Λ) of the cis-β isomer being in fast equilibrium with respect to the NMR tim…

Ethene/norbornene copolymerization with (isodicyclopentadienyl)titanium complex-MAO catalyst

2007

Norbornene (NB) homopolymerization and ethene/NB copolymerizations with a silylene-bridged (isodicyclopentadienyl)(tert-butylamido)titanium dichloride-methylalumoxane (MAO) catalyst system were investigated. This catalytic system shows no efficiency towards NB homopolymerization but produces poly(ethene-co-norbornene)s. An increase in the initial NB feed content leads to a loss of copolymerization activity as well as NB copolymer incorporation. The structure of the isodicyclopentadienyl fragment (IsodiCp) has a strong limiting effect on comonomer incorporation possibilities.

Ring opening polymerization of d,l-lactide and ε-caprolactone catalysed by (pyrazol-1-yl)copper(ii) carboxylate complexes

2021

1,2-Bis{(3,5-dimethylpyrazol-1-yl)methyl}benzene (L) reacts with [Cu(OAc)2] and C6H5COOH, 4-OH-C6H4COOH, 2-Cl-C6H4COOH and (3,5-NO2)2-C6H3COOH to afford the copper complexes [Cu2(C6H5COO)4(L)2] (1), [Cu2(4-OH-C6H4COO)4(L)2] (2), [Cu2(2-Cl-C6H4COO)4(L)2]n (3) and [Cu{(3,5-NO2)2-C6H3COO}2L]n (4) which are characterised by IR, mass spectrometry, elemental analyses, and X-ray crystallography. The structural data revealed two geometries that are adopted by the complexes: (i) paddle wheel in 1, 2·7H2O, 3 and (ii) regular chains in 3 and 4. Magnetic studies show strong antiferromagnetic couplings in the paddle wheel complexes and a weak antiferromagnetic coupling in the monometallic chain one. Cat…

Role of the Open-Shell Character on the Pressure-Induced Conductivity of an Organic Donor-Acceptor Radical Dyad

2018

Single‐component conductors based on neutral organic radicals have received a lot of attention due to the possibility that the unpaired electron can serve as a charge carrier without the need of a previous doping process. Although most of these systems are based on delocalized planar radicals, we present here a nonplanar and spin localized radical based on a tetrathiafulvalene (TTF) moiety, linked to a perchlorotriphenylmethyl (PTM) radical by a conjugated bridge, which exhibits a semiconducting behavior upon application of high pressure. The synthesis, electronic properties, and crystal structure of this neutral radical TTF‐Ph‐PTM derivative (1) are reported and implications of its crystal…

Gas phase heterogeneous partial oxidation reactions

2018

Abstract Mixed metal oxides are used as catalysts in the gas phase partial oxidation of hydrocarbons. This paper will present the principles of catalyst choice for selective oxidation reactions as well as the structural features of metal oxide catalysts. The nature of active sites in selective oxidation reactions will also be briefly discussed. We will pay special attention to several representative reactions: (1) ODH of short chain alkanes (from C1 to C4), (2) propene partial oxidation/ammoxidation on bismuth molybdate based catalysts, (3) n-butane direct oxidation to maleic anhydride on VPO type catalysts, and (4) propane direct oxidation/ammoxidation on mixed MoVTe(Sb)Nb–O catalysts. Fin…

A Selenium-Nitrogen Chain with Selenium in Different Oxidation States

2017

Conformational Control of Metallocene Backbone by Cyclopentadienyl Ring Substitution: a New Concept in Polyphosphane Ligands Evidenced by “Through-Sp…

2009

The present study deals with the conformational control of the metallocene backbone within ferrocenyl polyphosphane ligands and their performance in the highly topical palladium-catalyzed heteroaromatics arylation by direct C−H activation. New substituted cyclopentadienyl rings were synthesized, which allowed the assembling of original tri- and diphosphanes. The bulky cyclopentadienyl lithium salts diphenylphosphino-3-(triphenyl)methylcyclopentadienyllithium (4) and 1,2-bis(diphenylphosphino)-4-(triphenyl)methylcyclopentadienyllithium (5) were prepared in excellent yield. The assembling of these new hindered cyclopentadienyl salts (Cp) with other Cp fragments was performed in order to prepa…

The complementary structural studies of the double metal cyanide type catalysts for the ring opening polymerization of the oxiranes

2016

Strombolian eruptions and dynamics of magma degassing at Yasur Volcano (Vanuatu)

2020

Abstract Open vent basaltic volcanoes account for a substantial portion of the global atmospheric outgassing flux, largely through passive degassing and mild explosive activity. We present volcanic gas flux and composition data from Yasur Volcano, Vanuatu collected in July 2018. The average volcanic plume chemistry is characterised by a mean molar CO2/SO2 ratio of 2.14, H2O/SO2 of 148 and SO2/HCl of 1.02. The measured mean SO2 flux in the period of 6th to 9th July is 4.9 kg s−1. Therefore, the mean fluxes of the other species are 7.5 kg∙s−1 CO2, 208 kg∙s−1 H2O and 4.8 kg∙s−1 HCl. The degassing regime at Yasur volcano ranges from ‘passive’ to ‘active’ styles, with the latter including Stromb…

Application of entropic approach to estimate the mean flow velocity and Manning roughness coefficient in a high-curvature flume

2016

The entropy-based approach allows the estimation of the mean flow velocity in open channel flow by using the maximum flow velocity. The linear relationship between the mean velocity, umax, and the mean flow velocity, um, through the dimensionless parameter Φ(M), has been verified both in natural rivers and in laboratory channels. Recently, the authors of this study investigated the reliability of the entropy-based formula in a straight channel and under different bed and side-walls' roughness conditions. The present study aims to further validate the entropy-based approach and to explore the effectiveness of entropy-based formula in high curvature channels. Results show that as the effect o…