Abstract:The condensation of bis(o-formylphenyl) selenide with 1,2-diaminoethane or 1,3-diaminopropane yielded the new macrocyclic ligands 1 and 2 in very good yields. Crystals of 1 are monoclinic, space group P2 1 /c with a = 10.0648 (10)
“…The transannular Se···Se distance (4.75 Å) is longer than the Se···Se distance (3.808 Å) in the parent Schiff base 1. [7] The geometry around Se is V-shaped. The C(1B)-Se-C(1A) bond angle is 98.04°, which is smaller than that in the parent Schiff base (100.2°).…”
Section: Resultsmentioning
confidence: 99%
“…[5][6][7] The molecular structure of the ligand 4 (Figure 1, Table 1) is centrosymmetric, and only half of the molecule represents the asymmetric unit. The structure confirms the complete reduction of the Schiff base macrocycle.…”
Section: Resultsmentioning
confidence: 99%
“…[2,3] Only recently, some mixed donor macrocycles incorporating selenium and tellurium have been reported. [4][5][6][7] As part of our research on the design and synthesis of heavier chalcogenaaza macrocycles, we recently reported the synthesis and complexation studies of the selenaaza and telluraaza Schiff base macrocycles 1-3. [5][6][7] However, these Schiff base macrocycles are prone to transmetallation and hydrolysis on treatment with metal salts, which leads to cleavage of the macrocycle.…”
Section: Introductionmentioning
confidence: 99%
“…[5][6][7] However, these Schiff base macrocycles are prone to transmetallation and hydrolysis on treatment with metal salts, which leads to cleavage of the macrocycle. The selenaaza Schiff base macrocycle 1 forms the hydrolyzed product with the Pd II cation, [7] whereas the telluraaza Schiff base macrocycle 2 forms transmetallated products with Pt II and Hg II cations. [5] The hydrolysis of the selenaaza macrocycle 1 may be due to excessive strain on the ring, which is forced by the metal 172 tion by N2Te2 donor centers.…”
Section: Introductionmentioning
confidence: 99%
“…[4][5][6][7] As part of our research on the design and synthesis of heavier chalcogenaaza macrocycles, we recently reported the synthesis and complexation studies of the selenaaza and telluraaza Schiff base macrocycles 1-3. [5][6][7] However, these Schiff base macrocycles are prone to transmetallation and hydrolysis on treatment with metal salts, which leads to cleavage of the macrocycle. The selenaaza Schiff base macrocycle 1 forms the hydrolyzed product with the Pd II cation, [7] whereas the telluraaza Schiff base macrocycle 2 forms transmetallated products with Pt II and Hg II cations.…”
The chalcogenaaza macrocycles 4, 5 and 6 show versatility in ligation properties towards various transition metal ions. The structure of the reduced 22-membered selenaaza macrocycle 4 (C 32 H 36 N 4 Se 2 ) has been determined. The Ni II complex 7 exhibits coordination by the N4Se2 donor sites. The Pd II complexes 8, 9, 10, and 14 have been structurally characterized. The molecular structures of these complexes reveal interesting versatile ligating behaviors of the ligands. The Pd complexes 8, 9, and 14 display coordination by hard nitrogen donor atoms only, whereas the complex 10 showed coordina-
“…The transannular Se···Se distance (4.75 Å) is longer than the Se···Se distance (3.808 Å) in the parent Schiff base 1. [7] The geometry around Se is V-shaped. The C(1B)-Se-C(1A) bond angle is 98.04°, which is smaller than that in the parent Schiff base (100.2°).…”
Section: Resultsmentioning
confidence: 99%
“…[5][6][7] The molecular structure of the ligand 4 (Figure 1, Table 1) is centrosymmetric, and only half of the molecule represents the asymmetric unit. The structure confirms the complete reduction of the Schiff base macrocycle.…”
Section: Resultsmentioning
confidence: 99%
“…[2,3] Only recently, some mixed donor macrocycles incorporating selenium and tellurium have been reported. [4][5][6][7] As part of our research on the design and synthesis of heavier chalcogenaaza macrocycles, we recently reported the synthesis and complexation studies of the selenaaza and telluraaza Schiff base macrocycles 1-3. [5][6][7] However, these Schiff base macrocycles are prone to transmetallation and hydrolysis on treatment with metal salts, which leads to cleavage of the macrocycle.…”
Section: Introductionmentioning
confidence: 99%
“…[5][6][7] However, these Schiff base macrocycles are prone to transmetallation and hydrolysis on treatment with metal salts, which leads to cleavage of the macrocycle. The selenaaza Schiff base macrocycle 1 forms the hydrolyzed product with the Pd II cation, [7] whereas the telluraaza Schiff base macrocycle 2 forms transmetallated products with Pt II and Hg II cations. [5] The hydrolysis of the selenaaza macrocycle 1 may be due to excessive strain on the ring, which is forced by the metal 172 tion by N2Te2 donor centers.…”
Section: Introductionmentioning
confidence: 99%
“…[4][5][6][7] As part of our research on the design and synthesis of heavier chalcogenaaza macrocycles, we recently reported the synthesis and complexation studies of the selenaaza and telluraaza Schiff base macrocycles 1-3. [5][6][7] However, these Schiff base macrocycles are prone to transmetallation and hydrolysis on treatment with metal salts, which leads to cleavage of the macrocycle. The selenaaza Schiff base macrocycle 1 forms the hydrolyzed product with the Pd II cation, [7] whereas the telluraaza Schiff base macrocycle 2 forms transmetallated products with Pt II and Hg II cations.…”
The chalcogenaaza macrocycles 4, 5 and 6 show versatility in ligation properties towards various transition metal ions. The structure of the reduced 22-membered selenaaza macrocycle 4 (C 32 H 36 N 4 Se 2 ) has been determined. The Ni II complex 7 exhibits coordination by the N4Se2 donor sites. The Pd II complexes 8, 9, 10, and 14 have been structurally characterized. The molecular structures of these complexes reveal interesting versatile ligating behaviors of the ligands. The Pd complexes 8, 9, and 14 display coordination by hard nitrogen donor atoms only, whereas the complex 10 showed coordina-
In this chapter the major advances in the synthetic methodology and the syntheses of novel organoselenium compounds‐since 1987 are reviewed. These are presented in the order of oxidation states i.e. in the initial parts of the chapter developments in the area of the synthesis of low valent organoselenium compounds are discussed. These include: diselenides, selenides, selenols, selenolesters, selenones, selenocyanate, selenenyl halides and related derivatives. The latter part of the chapter deals with the syntheses of high valent i.e. selenium (IV) and selenium (VI) compounds.
Diselenides are generally prepared by the reaction of alkali metal chalcogenolates with appropriate organic halides. There has been a lot of activity in the area of the synthesis of selenides. The procedures include: epoxide ring opening, aziridine and other ring opening, addition to double and triple bonds, transition metal and Main Group Element catalyzed coupling reactions, nucleophilic substitution reactions, etc.
The novel compounds described include: selenocystine derivatives, chiral diselenides, triselenides, oranoselenenyl cations, selenium‐containing pincer ligands for catalysis, selenols and nitrososelenol derivatives, selenenyl azides. The chapter is based on over 350 original references.
and the synthesis and ethylene reactivity of two new nickel complexes [NiCl (py)(E,SO)] (Ni1, E = Se; Ni2, E = S) are reported. The minimum energy structures of the complexes were determined by density functional theory (DFT) calculations. For both compounds, the triplet and singlet 1 structures (with Cl trans to chalcogen) are higher in energy compared with singlet 2 (with Cl cis to chalcogen). Under initial catalytic condition (MAO, [Al/Ni] = 300, time = 20 min, T = 30 C) complex Ni1 oligomerizes ethylene with turnover frequencies (TOF) of 32.6 Â 10 3 (mol ethylene) (mol Ni) À1 (h) À1 with 81.3% of 1-butene production. The use of different cocatalyst systems (MAO/TMA or MAO/TiBA in an equimolar ratio) led to lower activities and poor selectivity for 1-C 4 . Under optimized reaction conditions (MAO, [Al/Ni] = 600, time-= 20 min, T = 30 C), the phenylthionyl complex Ni2 was 1.7 times more active than the phenylselenyl analog, with TOF of 72.3 Â 10 3 (mol ethylene) (mol Ni) À1 (h) À1 with 84.3% of 1-butene selectivity. DFT calculations suggest that the lowest lowest unoccupied molecular orbital (LUMO) energy and highest natural charge at the Ni center could be associated to the higher activity of Ni2 compared with the phenylselenyl analog Ni1.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.