Search results for "SUBSTITUTION"

SYNTHESIS, REACTIVITY OF ISOINDOLE DERIVATIVES

2004

Direct P-functionalization of azobenzene by a cationic phosphidozirconocene complex.

2016

International audience; We report that the cationic phosphidozirconocene complex [(eta(5)-C5H5)(2)Zr(PCy2)][CH3B(C6F5)(3)] (II) reacts with azobenzene, resulting in the expedient formation of Zr complex (2) bound to a tridentate PNN ligand. This reaction proceeds by a mechanism of cooperative nucleophilic substitution of hydrogen. The intermediate sigma(H) adduct (1) has been characterized by NMR spectroscopy.

An efficient method for selective oxidation of (oxime)Pt(II) to (oxime)Pt(IV) species using N,N-dichlorotosylamide

2016

The oxidation of (oxime)PtII species using the electrophilic chlorine-based oxidant N,N-dichlorotosylamide (4-CH3C6H4SO2NCl2) was studied. The reactions of trans-[PtCl2(oxime)2] (where oxime = acetoxime, cyclopentanone oxime, or acetaldoxime) with this oxidant led to trans-[PtCl4(oxime)2] products. The oxidation of trans-[Pt(o-OC6H4CH = NOH)2] at room temperature gave trans-[PtCl2(o-OC6H4CH = NOH)2], whereas the same reaction upon heating was accompanied by electrophilic substitution of the benzene rings. peerReviewed

Controlling Oxidative Addition and Reductive Elimination at Tin(I) via Hemi-Lability.

2021

We report on the synthesis of a distannyne supported by a pincer ligand bearing pendant amine donors that is capable of reversibly activating E–H bonds at one or both of the tin centres through dissociation of the hemi-labile N–Sn donor/acceptor interactions. This chemistry can be exploited to sequentially (and reversibly) assemble mixed-valence chains of tin atoms of the type ArSn{Sn(Ar)H} n SnAr ( n = 1, 2). The experimentally observed (decreasing) propensity towards chain growth with increasing chain length can be rationalized both thermodynamically and kinetically by the electron-withdrawing properties of the –Sn(Ar)H– backbone units generated via oxidative addition. peerReviewed

Human capital and the intertemporal substitution for leisure: empirical evidence for Spain

2022

AbstractIn this paper we provide the first estimate of the intertemporal substitution for leisure in Spain, accounting for the impact of human capital accumulation. This would allow uncovering whether the intertemporal labour supply of Spanish workers is affected by human capital. Our empirical strategy consists of estimating the equation for the intertemporal substitution of leisure with and without accounting for human capital, what allows to detect hypothetical estimation biases associated to omitting the impact of human capital. To that end, we build a pseudo-panel data set combining the Spanish Family Expenditure Survey and the Labour Survey over the period 1987–1997. While the model t…

Implementation of Substitution Treatment in Finland: Beyond Rationalisation and Medicalisation

2011

AIMS Finnish treatment of drug abuse has during the last two decades shifted from a predominantly psychosocial approach to a more medical mode. This is especially evident in the rapid implementation of substitution treatments (STs). My aim is to show that labelling this development as ‘medicalisation’ or ‘rationalisation’ as a form of medical progress will not increase our understanding of the change. MATERIAL AND DESIGN I analysed texts from several periodicals with psychosocial, social policy and medical perspectives between 1997 and 2005. Four basic conceptual and argumentative underpinnings emerged which gave credence to the medical and rationalapproach, and the validity of these four e…

Definition of Water Meter Substitution Plans based on a Composite Indicator

2014

This paper presents a water meter substitution plan based on a composite "Replacement indicator" which was defined and compared with common substitution strategies based on meter age and on run-to-fail approaches. The methodology was applied to one of the 17 sub-networks in which the Palermo city water distribution network (Italy) is divided. The analysis was carried out considering a substitution budget limitation and the results showed that the use of "Replacement indicator" outperform the classical substitution strategies based on meter age because it takes into account some other variables that may affect meter precision and wearing. (C) 2013 The Authors. Published by Elsevier Ltd.

Counting Berg partitions via Sturmian words and substitution tilings

2013

We develop the connection of Berg partitions with special substitution tilings of two tiles. We obtain a new proof that the number of Berg partitions with a fixed connectivity matrix is equal to half of the sum of its entries, [12]. This approach together with the formula of Seebold [10], for the number of substitutions preserving a given Sturmian sequence, shows that all of the combinatorial substitutions can be realized geometrically as Berg partitions. We treat Sturmian tilings as intersection tilings of bi-partitions. Using the symmetries of bi-partitions we obtain geometrically the palindromic properties of Sturmian sequences (Theorem 3) established combinatorially by de Luca and Migno…

The Impact of a 1,2,3-Triazole Motif on the Photophysical Behavior of Non-K Tetrasubstituted Pyrene with a Substitution Pattern Providing the Long Ax…

2022

1,3,6,8-Tetrasubstituted pyrene derivatives with two types of substituents (4-(2,2-dimethylpropyloxy)pyridine, 1-decyl-1,2,3-triazole, 1-benzyl-1,2,3-triazole, and pyrazole), substituted in such a way that provides the long axial symmetry, are prepared and characterized in the present study. To the best of our knowledge, the pyrene derivative containing the same heteroaryl motif (triazole) but substituted by two various alkyls, straight decyl and benzyl-based side chains (C), is reported for the first time. For comparison, compounds with one kind of triazole motif and substituted pyridine or pyrazole groups were prepared (A and B). The photophysical properties of all molecules were evaluate…

On the mechanism of imine elimination from Fischer tungsten carbene complexes

2016

(Aminoferrocenyl)(ferrocenyl)carbene(pentacarbonyl)tungsten(0) (CO)5W=C(NHFc)Fc (W(CO)5(E-2)) is synthesized by nucleophilic substitution of the ethoxy group of (CO)5W=C(OEt)Fc (M(CO)5(1Et)) by ferrocenyl amide Fc-NH– (Fc = ferrocenyl). W(CO)5(E-2) thermally and photochemically eliminates bulky E-1,2-diferrocenylimine (E-3) via a formal 1,2-H shift from the N to the carbene C atom. Kinetic and mechanistic studies to the formation of imine E-3 are performed by NMR, IR and UV–vis spectroscopy and liquid injection field desorption ionization (LIFDI) mass spectrometry as well as by trapping experiments for low-coordinate tungsten complexes with triphenylphosphane. W(CO)5(E-2) decays thermally i…