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The reaction of [MoCl(NO)Tp
* = tris(3,5-dimethylpyrazolylborate] with copper Schiff base complexes derived by condensation of one mole each of 2,5-dihydroxybenzaldehyde
and salicylaldehyde with α,ω diamines [NH2(CH2)
n
NH2, n = 2–4] yields heterobinuclear complexes with two potential redox centres. I.r., electronic and e.s.r. spectroscopic properties
of these complexes are described. Cyclic voltammetric data of the base complexes in DMSO reveal that the copper redox centres
undergo irreversible one electron reduction at potentials which vary slightly with the polymethylene carbon chain backbone
of the Schiff base ligands. Incorporation of [MoCl(NO)Tp
*]+ groups in the copper Schiff base complexes, results to a slight anodic shift (100 mV) in the reduction potential of the copper
centre which remains invariant as the polymethylene carbon chain lengthens. Electrochemical data of the heterobinuclear complexes
using CH2Cl2 and DMSO as solvents indicate the solvent dependence of the reduction potentials of these complexes. In CH2Cl2, the reduction potential of the copper centre shifts cathodically by 100 mV, while that of the molybdenum centre shifts anodically
by 200 mV. However, accumulated electrochemical data of the heterobinuclear complexes indicate minimal electronic interactions
between the copper and molybdenum redox centres.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
2.
Dr. Rajeev Rajasekharan‐Nair Annemarie Marckwordt Dr. Samuel T. Lutta Dr. Matthias Schwalbe Anne Biernat Dr. David R. Armstrong Dr. Allan J. B. Watson Dr. Alan R. Kennedy Dr. John Reglinski Dr. Mark D. Spicer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(40):13561-13568
Soft scorpionates have thus far been seen mainly as a family of ligands. Their chemistry is extended here to the production of novel cationic macrocycles using dihaloalkanes. By replacing the dihaloalkanes with mild oxidising agents (NO+, I2) we obtain two unique polycyclic heterocycles. The mechanism which leads to the formation of these polycyclic heterocycles is investigated using ab initio DFT calculations. 相似文献
3.
The reaction of 1 mol equivalent of MoCl2(NO)T*
p [T*
p = tris(3,5 dimethylpyrazolyl)borate] with one mole equivalent of the zinc Schiff base complexes obtained from the condensation of 2,5-dihydroxybenzaldehyde, salicylaldehyde and a series of , diamines [NH2(CH2)
n
NH2, n = 2–4] is described, together with the i.r.; u.v.–vis. and 1H-n.m.r. spectroscopic properties of these products. Cyclic voltammetric data in CH2Cl2 reveal that the binuclear complex products undergo reversible one-electron reductions associated with the MoCl(NO)T*
p centre. No zinc-based redox processes in the new complexes could be detected on the cyclic voltammetry timescale. The behaviour of the MoCl(NO)T*
p centre in DMSO indicates that the complexes undergo irreversible reductions at anodically shifted potentials (in comparison with the reduction of binuclear complexes in CH2Cl2), indicating that reductions of the binuclear complexes are solvent dependent. 相似文献
4.
Rajeev Rajesekharan‐Nair Samuel T. Lutta Alan R. Kennedy John Reglinski Mark D. Spicer 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(5):421-427
Reported here are the single‐crystal X‐ray structure analyses of bis‐μ‐methanol‐κ4O:O‐bis{[hydrotris(3‐phenyl‐2‐sulfanylidene‐2,3‐dihydro‐1H‐1,3‐imidazol‐1‐yl)borato‐κ3H,S,S′](methanol‐κO)sodium(I)}, [Na2(C27H22BN6S3)2(CH4O)4] (NaTmPh), bis‐μ‐methanol‐κ4O:O‐bis{[hydrotris(3‐isopropyl‐2‐sulfanylidene‐2,3‐dihydro‐1H‐1,3‐imidazol‐1‐yl)borato‐κ3H,S,S′](methanol‐κO)sodium(I)}–diethyl ether–methanol (1/0.3333/0.0833), [Na2(C18H28BN6S3)2(CH4O)4]·0.3333C4H10O·0.0833CH3OH (NaTmiPr), and a novel anhydrous form of sodium hydrotris(methylthioimidazolyl)borate, poly[[μ‐hydrotris(3‐methyl‐2‐sulfanylidene‐2,3‐dihydro‐1H‐1,3‐imidazol‐1‐yl)borato]sodium(I)], [Na(C12H16BN6S3)] ([NaTmMe]n). NaTmiPr and NaTmPh have similar dimeric molecular structures with κ3H,S,S′‐bonding, but they differ in that NaTmPh is crystallographically centrosymmetric (Z′ = 0.5) while NaTmiPr contains one crystallographically centrosymmetric dimer and one dimer positioned on a general position (Z′ = 1.5). [NaTmMe]n is a one‐dimensional coordination polymer that extends along the a direction and which contains a hitherto unseen side‐on η2‐C=S‐to‐Na bond type. An overview of the structural preferences of alkali metal soft scorpionate complexes is presented. This analysis suggests that these thione‐based ligands will continue to be a rich source of interesting alkali metal motifs worthy of isolation and characterization. 相似文献
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