Two categories of solid complexes were synthesized and characterized. The first type of solid complexes was prepared
in absolute EtOH while the second type was isolated from redistilled H2O. The complexes separated in presence
of H2O are accompanied by losing a proton from the carboxylic group as in case of Co2+ and Ni2+ complexes at pH = 8 using NaOH and NaOAc as buffering agents, respectively. On the other hand, the Co2+ and Ni2+ complexes separated in presence of absolute EtOH as a solvent and the ligand participates without losing a proton from the carboxylic group at pH above 8.
2.2.1. Synthesis of complexes in EtOH
A hot EtOH solution of the metal chlorides CuCl2·2H2O (1.0 mmol, 0.851 g), NiCl2·6H2O (0.59 g),
and CoCl2·6H2O (0.59 g) was added to hot solution of L (1.0 mmol, 0.896 g)
dissolved in EtOH (25 mL) and few drops of redistilled H2O. The pH of the reaction mixture was adjusted with
sodium acetate in case of Cu2+, while in case of Co2+ and Ni2+ complexes NaOH was used to raise
the pH of the reaction mixture up to 8. The reaction mixture was refluxed on hot plate for 3 h. The complexes formed
were filtered off, washed several times with EtOH and diethyl ether, and finally dried in vacuum desiccator over anhydrous
CaCl2. The Cu2+ complex is readily soluble in redistilled H2O and DMSO and partially soluble in EtOH and
DMF, but Ni2+ and Co2+ complexes are partially soluble in H2O, EtOH, DMSO, and DMF.
2.2.2. [Co(tric)2Cl2]·2.5H2O
Yield: 90%; brown powder; MP>300 °C. IR (KBr; cm−1): 3,415, 3,227 [OH (H2O)],
OH (EtOH), 2,966 (NH), 2,880 (OH, acid), 1,602 (CO), 521 (M−O). Calcd.: for C12H30CoN2O12Cl2 (%): C, 27.5; H, 5.76; Co,
11.24, Cl, 13.52. Found: C, 26.8; H, 5.46; Co, 11.49, Cl, 13.00. Λm (DMSO): 8 Ω−1cm2mol−1.
μeff: 5.1 BM. UV (cm−1): 25,252 (LMCT), 18,726 [4A2g(F) →4T1g(P);
ν3], 16,666 (4A2g→4T1g; ν2). The values of ν1 (4A2g→4T2g; ν1),
B, and β were calculated and found to be 8,928 cm−1, 400 cm−1, and 0.41, respectively. The β value indicates that the bond between the L and Co2+ ion is covalent
in nature.
2.2.3. [Cu(tric)2Cl2]·3H2O
Yield: 95%; torques powder; MP 195 °C. IR (KBr; cm−1): 3,322, 3,235 [OH (H2O)],
OH (EtOH), 2,895 (OH, acid), 2,968 (NH), 1,620 (CO), 557 (M−O). Calcd.: for C12H32CuN2O13Cl2 (%): C, 26.35;
H, 5.9; Cu, 11.62, Cl, 12.96. Found: C, 26.14; H, 5.42; Cu, 11.5, Cl, 13.3. Λm (DMSO):
65 Ω−1cm2mol−1. μeff: 2.3 BM.
UV (cm−1): 31,847 (LMCT), 12,626 (2Eg→2T2g). g// = 2.2, g⊥ = 2.11,
G = 2.578, and A = 97.5.
2.2.4. [Ni(tric)2Cl2(H2O)2]·H2O
Yield: 50%; grass green powder; MP>300 °C. IR (KBr; cm−1): 3,311, 3,423 [OH (EtOH)],
OH (H2O), 3,254 (NH), 2,870 (OH, acid), 1,612 (CO), 512 (M−O). Calcd.: for C12H32NiN2O13Cl2 (%): C, 26.59; H, 5.95;
Ni, 10.82, Cl, 13.08. Found: C, 26.45; H, 5.03; Ni, 11.4, Cl, 13.82. Λm (DMSO): 3 Ω−1cm2mol−1.
μeff: 4.13 BM. UV (cm−1): 29,940 (LMCT), 26,315
[3A2g→3T1g(P); ν3], 15,772 (3A2g→3T1g; ν2.
The values of ν1 (3A2g→3T2g), B, and β were calculated and found to be
9,968 cm−1, 812 cm−1, and 0.78, respectively. The value of
β suggests that the bond between the ligand and Ni2+ ion is mainly ionic in nature.
The complexes synthesized in the presence of H2O are completely different from the above solid complexes isolated
from EtOH. A hot aqueous solution of ZnCl2 (1.0 mmol, 0.68 g) was added to hot solution of tricine
(1.0 mmol, 0.90 g) dissolved in H2O (25 mL) and few drops of ethanol. The reaction mixture was
refluxed on hot plate for 6 h. The white product was filtered off and preserved in a desiccator over anhydrous
calcium chloride. Cadmium acetate (1.0 mmol, 1.33 g), NiCl2·6H2O (0.59 g), and CoCl2·6H2O
(0.59 g) were used to prepare the complexes using the same method of Zn2+ complex, but in the case
of Co2+ and Ni2+ the pH was raised to 8 using NaOAc; μeff diamagnetic in the
cases of Cd2+ and Zn2+ complexes.
2.3.1. [Cd(tric)2(Ac)2]·H2O
Yield: 95%; white powder; MP>238 °C. IR (KBr; cm−1): 3,430 (OH, H2O), 3,328
(OH, EtOH), 3,213 (NH), 2,922 (OH, acid), 1,604 (CO), 528 (M−O). Calcd.: for C16H34CdN2O15 (%): C, 31.66; H, 5.65; Cd,
18.52. Found: C, 31.07; H, 5.39; Cd, 18.08. Λm (DMSO): 0 Ω−1cm2mol−1,
Ueff: diamagnetic.
2.3.2. [Co(tric-H)2]·0.5H2O
Yield: 80%; simon powder; MP>300 °C. IR (KBr; cm−1): 3,323 (OH, H2O), 3,226
(OH, EtOH), 2,969 (NH), 2,828 (OH, acid), 1,614 (CO), 521 (M−O). Calcd.: for C12H25CoN2O21/2 (%): C, 33.97; H, 5.93;
Co, 13.89. Found: C, 33.97; H, 6.16; Co, 13.65. Λm (DMSO): 2 Ω−1cm2mol−1.
μeff: 4.6 BM. UV (cm−1): 23,041 (LMCT), 18,656 [4A2g(F) →4T1g(P);
ν3], 16,756 (4A2g→4T1g; ν2). The values of ν1 (4A2g→4T2g), B, and β
were calculated and found to be 8,917 cm−1, 413 cm−1, and 0.42,
respectively. The value of β suggests that the bond between the ligand and Co2+ ion is covalent in nature.
2.3.3. [Ni(tric-H)2(H2O)2]
Yield: 50%; pale blue powder; MP>300 °C. IR (KBr; cm−1): 3,332 (OH, H2O),
3,213 (OH, EtOH) 2,976 (NH), 2,890 (OH, acid), 1,601 (CO), 523 (M−O). Calcd.: for C12H28NiN2O12 (%): C, 31.95; H, 6.25;
Ni, 13.01. Found: C, 32.38; H, 6.23; Ni, 13.8. Λm (DMSO): 0 Ω−1cm2mol−1.
μeff: 3.79 BM. UV (cm−1): 24,752 [3A2g→3T1g(P); ν3], 15,479
(3A2g→3T1g; ν2). The values of ν1 (3A2g→3T2g),
B, and β were calculated and found to be 10,466 cm−1, 589 cm−1, and 0.66, respectively. The value of β suggests that the bond between the ligand and Ni2+ ion is
intermediate in nature.
2.3.4. [Zn(tric)2Cl2]·EtOH
Yield: 95%; white powder; MP>300 °C. IR (KBr; cm−1): 3,346 (OH, EtOH), 3,105 (NH),
2,868 (OH, acid), 1,614 (CO), 504 (M−O). Calcd.: for C14H32ZnN2O11Cl2 (%): C, 31.1; H, 5.96; Zn, 12.09, Cl, 13.11.
Found: C, 31.21; H, 5.63; Zn, 12.03. Λm (DMSO): 0 Ω−1cm2mol−1.
μeff: diamagnetic.