1Faculy of Science and Technology, Deparement of chemesry, Mineral and Analyical Chemestry Laboratory, Cheikh Anta Diop Universiy, Senegal
2Faculy of Science and Technology, Deparement of chemesry, Laboraory of Organic Physical Chemestry Instrumental Analysis, Cheikh Anta Diop Universiy, Senegal
Submission: February 08, 2020; Published: February 20, 2020
*Corresponding author: Dame Seye, Faculy of Science and Technology, Deparement of chemesry, Mineral and Analyical Chemestry Laboratory, Cheikh Anta Diop Universiy, Dakar, Senegal
How to cite this article: Dame S, Assane T, Momath L, Mouhamadou B D, Cheikh A K D, et al. New MCl3 (M = Y, Dy, Pr) Salicylato, Maleato, Phtalato, Phenylsufonato and Phosphato Complexes and Adducts: Synthesis and Infrared Study. Organic & Medicinal Chem IJ. 2020; 9(3): 555761. DOI: 10.19080/OMCIJ.2019.09.555761
Nine rare earth complexes have been synthesized from reaction carried in common organic solvent between salicylate, maleate, phtalate, phenylsulfonate or phosphate ammonium salt and MCl3 (M = Y, Dy, Pr). All compounds have been structurally characterized by infrared. Structures involving the complex anions have been proposed. The suggested structures are discrete or of double metallic components type. The oxyanions behave towards metallic centres as monodentate, monochelating or monochelating and monodentate ligands. The coordination number at rare earth metal atoms vary from five (5) for Pr and Dy to twelve (12) for Dy. For compounds containing a protonated amine, when the possible hydrogen bonding interactions are considered supramolecular architectures may be obtained.
A great variety of transitional and non-transitional metal and non-metal compounds have been synthetized using as starting materials protonated amine salts in general soluble in organic solvents [1-3]. In rare earth halide organometallic compounds, these protonated amine salts can be involved in hydrogen bonds to lead to supramolecular architectures [4-6]. The ability of these cations to form supramolecular structures has been highly noted for numerous complexes with rare earths (lanthanides) [7,8].
In this dynamic salts of salicylic, Phtalic, maleic, phenyl sulfonic and phosphoric acids with dibutylamine, mono cyclohexylamine and diisopropylamino have been prepared and their reactions with trihalides of rare earths, in the purpose of studying the structural arrangements of the obtained complexes and deducing the coordinating ability of oxyanions, have been undertaken. This study has yielded nine new compounds; infrared characterization of which have been carried out then structures suggested on the basis of infrared data.
All the chemicals were purchased from Aldrich Company (Germany) and used without any further purification.
Bu2NH2C6H4(OH)CO2 (L1), Bu2NH2(C6H4(CO2)2 (L2), (CyNH3)2.O2C(CH)2CO2 (L3), Bu2NH2C6H5SO3 (L4), iPr2NH2C6H5SO3 (L5), and (CyNH3)H2PO4 (L6 ) have been obtained as powders on allowing to react in methanol:
L1: dibutylamine (Bu2NH2) and salicylic acid in a 1:1 ratio
L2: dibutylamine (Bu2NH2) and phtalic acid in a 2:1 ratio
L4: dibutylamine (Bu2NH2) and phenylsulfonic acid in a 1:1 ratio
L5: diisopropylamine (iPr2NH) and phenylsulfonic acid in a 1:1 ratio
L6: monocyclohexylamine (CyNH2) and phosphoric acid in a 1:1 ratio
The compounds A, B, C, D, E, F, G, H and I were obtained as
white powders after a slow solvent evaporation at room temperature
on allowing to react in methanol: L1 and PrCl3 in a 1:1 ratio
(A), L2 and Y(CH3CO2)3 in a 1:1 ratio (B), L2 and YCl3 in a 1:1 ratio
(C), L2 and DyCl3 in a 1:1 ratio (D), L3 and DyCl3 in a 1:1 ratio (E),
L4 and Y(CH3CO2)3 in a 1:1 ratio (F), L4 and Dy Cl3 in a 1:1 ratio (G),
L5 and Y(CH3CO2)3 in a 1:1 ratio (H) and, L6 and DyCl3 in a 1:1 ratio
(I). All solutions were stirred around two hours before being submitted
to a slow solvent evaporation.
The analytical data [% calculated (% found)], have allowed
to suggest the following formulae (Table 1). The infrared spectra
were recorded on a Bruker Vector 22 spectrometer equipped
with a Specac Golden Gate™ ATR device. Infrared data are given in
cm-1 [IR abbreviations: (vs) very strong, (s) strong, (m) medium].
Elemental analyses were performed at the “Institut de Chimie
Moléculaire”, University of Burgundy, Dijon-France. All chemicals
were purchased from Sigma-Aldrich Chemie GmbH, Steinheim,
Germany and used without any further purification. Let us consider
the main IR data (Tables 2-4) of compounds A-I.
From these infrared data we have suggested while considering
the complex anion of the studied complexes and adducts: For A, a
discrete structure with an Y3+ ion chelated by three acetate and the
salicylate anions conferring a coordination number of eight (8) to
the Y3+ ion (Figure 1). For B, C and D which have the same formula (Bu2NH2)4[(C6H4(CO2)2)2.3MCl3] and M = Dy, Y or Pr, we will consider
one of them as the relative molecule. As structure, we can
consider a central PrCl3 molecule monocoordinated to each of the
phtalate ions providing a coordination number of five (5) to the
Pr3+ center. The external PrCl3 are each one mono chelated by the
carboxylate group not involved in the coordination of the central
PrCl3 molecule. Thus, all metal centers have a coordination number
of five (5) (Figure 2).
For F, the suggested structure is discrete with a metal center
mono chelated by acetate and sulfonate anions, the coordination
number around yttrium being eight (8) (Figure 4). For G or H, the
proposed structure is like that suggested for E by replacing male ates with phenyl sulfonates (Figure 5) or dihydrogen phosphates
(Figure 6). For I, the structure consists of a Y3+ coordinated to a
water molecule and mono chelated by the H2PO4- and the acetate
anions giving to the yttrium a coordination number of nine (9)
(Figure 7). NB: in all these studied compounds while considering
the involvement of the cation through hydrogen bonds a supramolecular
architecture may be obtained.
We have synthesized and studied nine new complexes and adducts
of rare earth metals containing carboxylate, phosphate and
phenyl sulfonate anions. The studied compounds have allowed
proposing monomeric and double metallic components structures.
The presence of the complex-ion [M3Cl8]- in several compounds
and a double metal component is noteworthy. The coordination
number of the metal center of the second metal component
may exceed ten (10).
M Biagini Cingi, A M Manotti Lanfredi, A Tiripicchio, M Tiripicchio Camellini (1978) The crystal and molecular structures of magnesium di-o-phthalatocuprate (II) dihydrate and strontium di-o-phthalatocuprate (II) trihydrate. B 34: 406-411.