A DFT Study of Structural and Bonding Properties of Complexes Obtained from First-Row Transition Metal Chelation by 3-Alkyl-4-phenylacetylamino-4,5-dihydro-1H-1,2,4-triazol-5-one and Its Derivatives

Table 1

Selected B3LYP/Mixed I level: bond lengths (Ǻ), bond angles (degree), and dihedral angles (degree) for neutral ADPHT ligand-metal complexes in various media.

	Fe^2+			Ni^2+			Cu^2+			Cu^+			Zn^2+
Parameters	1a	1b	1c	2a	2b	2c	3a	3b	3c	4a	4b	4c	5a	5b	5c
gas
M^2+-O2	1.840	1.836	1.835	1.837	1.836	1.835	2.061	2.046	2.040	1.998	1.999	1.999	1.906	1.906	1.905
M^2+-O3	1.818	1.810	1.806	1.827	1.820	1.819	1.969	1.969	1.969	1.995	1.986	1.986	1.899	1.898	1.899
O2-M^2+-O3	105.4	105.8	105.8	102.6	102.1	102.1	98.5	98.5	98.3	105.6	106.2	105.6	106.1	106.1	106.4
N1-C3-O3-M^2+	27.2	24.5	23.4	54.4	−57.3	57.9	57.4	59.1	59.0	51.1	51.6	53.4	42.7	44.9	45.5
N3-C2-O2-M^2+	33.7	31.7	31.0	35.0	−35.6	35.5	53.1	53.3	52.1	53.3	53.5	54.0	44.9	42.3	42.4
N1-N3-C2-O2	12.6	12.3	12.1	11.9	−11.5	11.7	5.7	5.0	6.1	7.7	7.5	7.1	9.8	10.0	9.8
Water
M^2+-O2	1.920	1.925	1.933	1.854	1.863	1.865	1.954	1.951	1.955	2.029	2.035	2.038	2.048	2.047	2.071
M^2+-O3	1.929	1.916	1.932	1.838	1.829	1.835	1.933	1.927	1.928	2.022	2.016	2.019	2.032	2.055	2.023
O2-M^2+-O3	99.7	98.2	97.8	97.9	98.3	98.2	101.0	99.7	99.8	103.5	102.9	102.3	90.7	91.1	91.3
N1-C3-O3-M^2+	44.4	40.9	48.5	64.3	−66.4	66.7	58.6	60.8	63.0	54.5	56.9	59.8	64.3	57.6	66.5
N3-C2-O2-M^2+	47.5	50.9	54.1	22.8	−36.0	37.2	43.8	44.6	47.6	60.6	61.5	61.8	63.2	66.1	62.0
N1-N3-C2-O2	14.1	14.4	11.4	13.4	52.0	10.1	13.6	14.6	11.4	5.7	4.2	3.2	1.0	5.0	1.0
Benzene
M^2+-O2	1.865	1.868	1.871	1.833	1.843	1.841	2.042	2.019	2.018	2.012	2.018	2.018	—	1.944	1.949
M^2+-O3	1.850	1.846	1.846	1.829	1.818	1.820	1.971	1.972	1.970	2.007	2.001	2.001	—	1.928	1.932
O2-M^2+-O3	102.6	102.8	103.3	99.6	100.9	100.9	98.9	99.7	98.5	104.5	103.5	103.2	—	101.9	102.3
N1-C3-O3-M^2+	131.8	32.9	35.4	59.9	−58.5	59.8	58.3	59.2	61.3	52.7	55.9	57.5	—	42.5	48.4
N3-C2-O2-M^2+	36.1	40.3	38.5	27.9	−31.8	34.7	53.2	50.6	54.7	55.4	58.6	58.6	—	40.8	42.9
N1-N3-C2-O2	13.9	14.6	13.1	9.3	−14.0	13.6	5.8	7.2	5.2	9.8	4.6	4.7	—	13.6	9.7
DMF
M^2+-O2	1.918	1.923	1.909	1.852	1.861	1.857	1.958	1.955	1.958	2.028	2.034	2.037	2.043	2.050	2.058
M^2+-O3	1.926	1.912	1.902	1.837	1.828	1.828	1.937	1.930	1.931	2.021	2.015	2.019	2.027	2.042	2.003
O2-M^2+-O3	99.6	116.8	100.2	98.1	98.4	98.4	101.0	100.9	99.8	103.6	103.0	102.2	90.9	91.0	91.4
N1-C3-O3-M^2+	42.4	50.0	38.4	63.9	−66.2	65.7	58.3	60.5	62.9	54.4	56.9	59.8	64.0	57.6	62.8
N3-C2-O2-M^2+	48.1	40.4	39.9	23.5	−35.6	34.8	44.4	44.8	47.7	60.5	61.0	61.6	63.1	65.8	64.2
N1-N3-C2-O2	13.6	14.6	16.6	13.5	−9.5	9.7	13.3	14.5	11.3	5.6	4.5	3.3	1.0	5.0	3.0