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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 323-337 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solution chemistry of Cu(II) with a series of five planar tridentate nitrogen ligands, 2,6-bis(benzimidazol-2-yl)pyridine (bzimpy, 1), 2,6-bis(l-methylbenzimidazol-2-yl)pyridine (mbzimpy, 2) 2,6-bis(benzothiazol-2-yl) pyridine (bzthpy, 3), 2,6-bis(benzoxazol-2-yl)pyridine (bzoxpy, 4), and 2,2′, 6′, 2″-terpyridyl (terpy, 5) is reported. Electronic and EPR spectra are consistent with the complexes [CuL]2+ having essentially tetragonal structure in solution, with the fourth coordination site in the plane of the ligand occupied by solvent. bzthpy and bzoxpy show smaller ligand-field splittings than bzimpy, mbzimpy, and terpy, and are easily decomplexed from the copper. Substitution of the coordinated solvent molecule in the plane of the ligand is observed with Cl- and OH- (provided that the ligand has no acidic protons) for all ligands except terpy. The reaction between [Cu(mbzimpy)]2+ and imidazole has been studied by potentiometric titration in MeCN/H2O 1:1 and shows strong binding of the imidazole in the plane (log K = 4.5 at 25°), and also the formation of an imidazolate-bridged dinuclear species.
    Additional Material: 3 Ill.
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  • 2
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title compound and its potassium analog have been prepared from corresponding aqueous solutions of 99TcO4-; at pH ≍ 2 with SO2 as a reducing agent. An X-ray structure determination of the Na-salt showed Tc coordinated to the tetradentate N(CH2COO)33- ligand (NTA). Two Tc-NTA moieties are joined via two bridging O-atoms into a four-membered Tc2O2 ring. The observed diamagnetism, a strong absorption band at 19 950 cm-1, and a short Tc-Tc distance of 2.363 Å are typical for the Tc2O2-fragment with its strong metal-metal interaction. The structural trans-influence at Tc and the network of H-bonds are consistent with Tc in oxidation state IV.
    Additional Material: 1 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 1063-1069 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ligand 2,2′,2″-nitrilotriphenol reacts with P(III) and P(V) compounds to form corresponding phosphorus complexes. Syntheses and NMR data of 2,2′,2″-nitrilotriphenyl phosphite (II), 2,2′,2″-nitrilotriphenyl phosphate (III) and of a hydrolysis product of II, 2,2′-[N-(2-hydroxyphenyl)imino]diphenly phosphonate (IV), are reported, as well as crystal structures of II and IV. Phosphite II shows a bicycloundecane framework; no NċPinteraction is present. The phosphonate IV shows two coordinated and one dangling phenol group; the N-atom does not interact with the P-atom. Strong acids protonate II as well as III to form cations: in these, NMR evidence indicates coordination of the N-atom to the P-atom.
    Additional Material: 2 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 499-510 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The tetradentate ligand 2,2′,2″-nitrilotriphenol forms a boron complex III with an intramolecular, transannular N→B dative bond of 1.68 Å in a strained tricyclo[3.3.3.0]undecane chelating system. The complex reacts with nitrogen bases L, such as pyridine, quinuclidine and others, to form complexes III-L, in which the intramolecular B-N bond is replaced by one between B and the external nucleophile. In solution, this displacement reaction is reversible. It was studied by temperature-dependent NMR spectroscopy. The resulting reaction and activation parameters suggest that the reaction is a bimolecular nucleophilic substitution (SN2).
    Additional Material: 7 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 511-519 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Crystal and molecular structures of a complex between B(III) and the tripod ligand 2,2′,2″-nitrilotriphenol as well as of its pyridine and quinuclidine adducts are presented. The 2,2′,2″-nitrilotriphenyl borate (III) molecule shows a strained, tricyclic chelate system with a central N-B donor-acceptor bond of 1.681(5) Å. In the adducts with pyridine (IV) and quinuclidine (III-quin), this bond is broken, the N-atom inverts and is pushed out of the coordination sphere (B-Nintern = 2.82 Å for Py and 2.85 Å for quin), and a new bond is formed between the boron atom and the external nucleophile (B-Nextern = 1.631 Å for Py and 1.643 Å for quin).
    Additional Material: 3 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 70 (1987), S. 520-533 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Crystal and molecular structures of three Al(III) complexes of the tripod ligand 2,2′,2″-nitrilotriphenolate (I) are presented. They all show 5-coordinate Al in approximately trigonal bipyramidal geometry, with an external nucleophile X occupying the second axial position. X is OH- in[Al(I)(OH)]-[Hquin]+ (quin = quinuclidine), N in [Al(I)(py)] (py = pyridine), and one of the O-atoms of a second molecule in the dimeric [(Al(I))2]. Correlated variations in the axial bond lengths of the trigonal bipyramid are observed: [(Al(I))2]: Al-Nint. = 2.094 Å, Al-Oext. = 1.850 Å; [Al(I)(py)]: Al-Nint. = 2.153 Å, Al-Next., = 1.992 Å; [Al(I)(OH)]-: Al-Nint. = 2.278 Å, Al-Oext. = 1.765 Å. They are interpreted in terms of a dissociative reaction path at the Al(III) centre.
    Additional Material: 6 Ill.
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