Coordination Compounds of Substituted 1,lO-Phenanthrolines and Related Dipyridyls. IV. Physicochemical Study of Complexes of Copper and 2,9-Dimethyl-1,10-phenanthroline

1963 ◽  
Vol 16 (1) ◽  
pp. 34 ◽  
Author(s):  
JR Hall ◽  
NK Marchant ◽  
RA Plowman

The magnetic susceptibilities, conductivities, and infrared spectra of some complexes of copper and 2,9-dimethyl-1,10-phenanthroline (dmp) have been obtained. The magnetic moments of the copper(II) compounds lie in the range 1.9 to 2.0 B.M. Complexes of formula CudmpX2, where X = NO3, Cl, and Br, are nonelectrolytes in nitrobenzene. The substances Cu(dmp)2X2H2O and hydrated forms of the compounds Cu(dmp)2XClO4, where X = NO3, Cl, and Br behave as 1 : 1 electrolytes. The copper(II) ion in the bis complexes is at least five-coordinate and it is proposed that the donor nitrogen atoms take up a flattened tetrahedral arrangement. The complexes of formula Cu(dmp)2X, where X = NO3, ClO4, Cl, Br. I, and I3 are diamagnetic solids, 1 : 1 electrolytes in nitrobenzene, and are expected to have a tetrahedral arrangement of the four donor nitrogen atoms about the copper atom. The mono complexes CudmpX, where X = Cl, Br, and I are diamagnetic, practically insoluble in organic solvents, and probably dimeric with a tetrahedral arrangement of the ligand donor atoms.

1970 ◽  
Vol 23 (4) ◽  
pp. 691 ◽  
Author(s):  
EW Ainscough ◽  
RA Plowman

Solutions of 2-methyl-1,10-phenanthroline (rnep) with excess copper(II) salts in organic solvents yielded complexes of the formula Cu(mep)X2 (X = NO3, Cl, Br, I). These were non-electrolytes in nitrobenzene. When excess rnep was present bis- complexes of the type Cu(mep)2Cl2,6H2O, Cu(mep)2/sub>(NO3)2,H2O, and hydrated forms of the type Cu(mep)2XClO4 (X = Cl, NO3) were obtained. These were 1 : 1 electrolytes in nitrobenzene and the copper(II) ion was at least five-coordinated with the donor nitrogen atoms taking up a flattened tetrahedral arrangement. Hydrated copper(II) perchlorate with rnep in a 1 : 2 or 1 : 1 ratio yielded Cu(mep)2(ClO4)2,2H2O which is a 2 : 1 electrolyte in nitrobenzene. From a water solution of copper nitrate and rnep in the ratio 1 : 3.5, a complex Cu(mep)3(ClO>sub>4)2 precipitated upon the addition of a sodium perchlorate solution. I t was thought previously that this compound did not exist. The magnetic susceptibilities, the conductivities, and the visible, absorption, and infrared spectra of some rnep complexes have been obtained and structures are proposed from this information.


1965 ◽  
Vol 18 (9) ◽  
pp. 1339 ◽  
Author(s):  
JR Hall ◽  
MR Litzow ◽  
RA Plowman

A number of diamagnetic complexes of copper(I) and 4,6,4',6'-tetramethyl-2,2'-bipyridine (tmb) have been prepared and some physical properties measured. The complexes of formula Cu(tmb)2X where X = NO3, ClO4, Br, and I behave as 1 : 1 electrolytes in nitrobenzene and nitromethane, while the complex Cu(tmb)2Cl,H2O apparently undergoes partial dissociation in these solvents. All are expected to have a tetrahedral arrangement of the four donor nitrogen atoms about the copper atom. The mono complexes CuXtmb, where X = Cl, Br, and I, appear to be dimeric in the solid state with halogen bridging, but in solution the chloro and bromo complexes rearrange to varying degrees depending on the solvent, forming the salt-type compounds [Cu(tmb)2][CuX2]. CuItmb is insoluble in all common solvents.


1965 ◽  
Vol 18 (9) ◽  
pp. 1345 ◽  
Author(s):  
JR Hall ◽  
RA Plowman ◽  
HS Preston

Addition of 2,9-dimethyl-1,10-phenanthroline (dmp) in organic solvents to aqueous solutions of silver(1) salts yielded mono complexes represented by AgXdmp, where X = NO3, Cl, Br, I; 2X = SO4, and bis complexes Ag(dmp),Y, where Y = NO3, Cl04. Water of crystallization was present only in the sulphate. The mono complexes were empirically three-coordinate. Low solubility prevented the determination of molecular weights. Infrared spectra indicated that the polyatomic anions were covalently bound. The 1 : 1 electrolyte [Ag(dmp)(py)]ClO4 subsequently prepared seemed to be an example of three-coordination. The bis complexes were 1 : 1 electrolytes in nitrobenzene and were most likely tetrahedral.


1963 ◽  
Vol 41 (4) ◽  
pp. 876-882 ◽  
Author(s):  
R. C. Aggarwal ◽  
M. Onyszchuk

Silicon tetrafluoride and hydrazine react in a vacuum to produce a white, non-volatile, solid, 1:2 complex, SiF4.2N2H4. This compound sublimes with decomposition above 200° and is insoluble in common organic solvents. It reacts with (a) 55% hydrofluoric acid, (b) anhydrous hydrogen chloride, (c) ethylenediamine, (d) ammonia, and (e) boron trifluoride, producing: (a) (N2H5+)2SiF62−, (b) N2H5+Cl−, (c) SiF4.NH2(CH2)2NH2, (d) SiF4.2NH3, and (e) BF3.N2H4. A comparison of the infrared spectra of SiF4.2NH3, SiF4.2N2H4, and SiF4.NH2(CH2)2NH2 suggests that all three complexes have cis octahedral structure.


1965 ◽  
Vol 18 (5) ◽  
pp. 691 ◽  
Author(s):  
DB Fox ◽  
JR Hall ◽  
RA Plowman

A series of complexes of cobalt(II) and 2,9-dimethyl-1,10-phenanthroline (dmp) has been prepared. Complexes of formula CoX2dmp (X = Cl, Br, I, KCS) are monomeric in acetone and camphor and non-electrolytes in nitrobenzene and nitromethane. The magnetic moments and visible absorption spectra favour the assignment of tetrahedral stereochemistry about the Co atom. Complexes containing 2 moles dmp per Co appear to have octahedral arrangements of ligands about the Co atom. These are of the type [CoNO3(H2O)dmp2]X, (X = NO3, ClO4, BPh4) and Co(NCS)2dmp2. The magnetic moments, visible and infrared spectra, and conductances in nitrobenzene and nitromethane support this conclusion. With other mono-dmp complexes (CoX2dmp, X = NO3, �SO4) and bis-dmp complexes {CoXdmp,ClO4,H2O (X = Cl, Br) ; Codmp2(ClO4)2}, stereochemical assignments could not be made.


1957 ◽  
Vol 10 (4) ◽  
pp. 386 ◽  
Author(s):  
M Kishita ◽  
Y Muto ◽  
M Kubo

The magnetic susceptibilities of salicylal-o-hydroxybenzylamine Cu(II), salicylal-o-hydroxyanil Cu(II), acetylacetone-mono-(0-hydroxyanil) Cu(II), and benzoylacetone- mono-(0-hydroxyanil) Cu(II), as well as their pyridinates, have been measured by the Gouy method at room temperature. The effective magnetic moments calculated from the . data of the pyridine-free complexes per one copper atom are smaller than the theoretical moment, 1.73 B.M., for one odd electron. Although it has been presumed from the method of synthesis, the chemical analysis of the complexes, and the tridentate nature of the ligand molecules that the copper atoms of the chelates have the unusual coordination number 3, the subnormal magnetic moments suggest the presence of dimeric molecules, in which two copper atoms are very close to each other as in cupric acetate monohydrate. On the other hand, the pyridinates have normal magnetic moments expected for tetra-coordinated copper complexes.


1962 ◽  
Vol 15 (2) ◽  
pp. 235 ◽  
Author(s):  
DB Fox ◽  
JR Hall ◽  
RA Plowman

A number of mono and bis(che1ate) complexes of iron(II) and 2,9-dimethyl-1,10-phenanthroline (dmp) have been isolated. The mono complexes are of general formula FedmpX2, where X=Cl, Br, I ; 2X=SO4. They are yellow to brown in colour except for the sulphato complex, which is pink. Conductivity and cryoscopic measurements indicate that the halogeno compounds are nonelectrolytes and monomeric. The magnetic moments range from 5.1 to 5.4 B.M. The evidence points to these compounds being four-coordinate tetrahedral complexes. The bis(che1ate)complexes are Fe(dmp)2(NO3)2(H2O)2 and Fe(dmp)2(NO3)(ClO4)(H2O)2, both yellow crystalline substances. They are 1 : 1 electrolytes in nitrobenzene and nitromethane. The magnetic moments are 5.2 B.M. for the dinitrate and 5.05 B.M. for the nitrate-perchlorate. According to their infrared spectra, each compound in the solid state appears to contain covalently bound nitrate and is most probably six-coordinate.


2008 ◽  
Vol 59 (7) ◽  
Author(s):  
Madalina Angelusiu ◽  
Maria Negoiu ◽  
Stefania-Felicia Barbuceanu ◽  
Tudor Rosu

The paper presents the synthesis and characterization of Cu(II), Co(II), Ni(II), Cd(II), Zn(II) and Hg(II) complexes with N1-[4-(4-bromo-phenylsulfonyl)-benzoyl]-N4-(4-methoxyphenyl)-thiosemicarbazide. The new compounds were characterized by IR, EPR, electronic spectroscopy, magnetic moments, thermo-gravimetric analysis and elemental analysis.


Sign in / Sign up

Export Citation Format

Share Document