Reactions of Cp2MCl2 (M=Ti or Zr) with Imine-Oxime Ligands. Formation of Metallacycles
Abstract
:Introduction
Results and Discussion
Reactants (molar ratio) | Time (h) | Product; Yield (%) | Colour | Found (calcd.) % | |||
---|---|---|---|---|---|---|---|
C | H | N | M | ||||
Cp2TiCl2+L1H2+Et3N (1 : 1 : 2) | 10 | [Cp2Ti(L1)], 68 | Yellow | 75.4 (75.6) | 4.8 (4.9) | 7.8 (8.0) | 6.8 (6.8) |
Cp2ZrCl2+L1H2+Et3 N(1 : 1 : 2) | 12 | [Cp2Zr(L1)], 65 | Dark brown | 71.0 (71.2) | 4.4 (4.6) | 7.3 (7.5) | 12.2 (12.3) |
Cp2TiCl2+L2H2+Et3N (1 : 1 : 2) | 10 | [Cp2Ti(L2)], 70 | Dark brown | 75.3 (75.6) | 4.6 (4.9) | 7.8 (8.0) | 6.8 (6.8) |
Cp2ZrCl2+L2H2+Et3N (1 : 1 : 2) | 12 | [Cp2Zr(L2)], 60 | Yellowish brown | 71.0 (71.2) | 4.4 (4.6) | 7.4 (7.5) | 12.1 (12.3) |
Cp2TiCl2+L3H2+Et3N (1 : 1 : 2) | 12 | [Cp2Ti(L3)], 68 | cream | 75.5 (75.8) | 5.0 (5.1) | 7.6 (7.9) | 6.6 (6.7) |
Cp2ZrCl2+L3H2+Et3N (1 : 1 : 2) | 14 | [Cp2Zr(L3)], 60 | Light brown | 71.4 (71.5) | 4.8 (4.9) | 7.3 (7.4) | 12.0 (12.0) |
Cp2TiCl2+L4H2+Et3N (1 : 1 : 2) | 15 | [Cp2Ti(L4)], 62 | Light brown | 73.6 (73.8) | 4.6 (4.7) | 9.8 (10.0) | 6.7 (6.8) |
Cp2ZrCl2+L4H2+Et3N (1 : 1 : 2) | 15 | [Cp2Zr(L4)], 58 | Dark brown | 69.3 (69.5) | 4.4 (4.5) | 9.2 (9.4) | 12.3 (12.3) |
- L1H2 = ligand derived from benzil-α-monoxime and 2-phenylenedianine
- L2H2 = ligand derived from benzil-α-monoxime and 4-phenylenedianine
- L3H2 = ligand derived from benzil-α-monoxime and 4-methyl-2-phenylenedianine
- L4H2 = ligand derived from benzil-α-monoxime and 2,6-diaminopyridine
Complex | IR | 1H NMR | Aromatic ring | |||
---|---|---|---|---|---|---|
η5-C5H5 | υ(C=N) | υ(N-O) | υ(M-O) | η5-C5H5 | ||
[Cp2Ti(L1)] | 3000s, 1420m, 1025m | 1620s, 1585m | 1230m | 440m | 6.80s | 7.65-7.82m |
[Cp2Zr(L1)] | 3000s, 1425m, 1020m | 1610s, 1580m | 1225m | 430m | 6.68s | 7.50-7.80m |
[Cp2Ti(L2)] | 3010s, 1410m, 1020m | 1615s, 1575m | 1235m | 445m | 6.85s | 7.70-7.85m |
[Cp2Zr(L2)] | 3015s, 1420m, 1015m | 1620s, 1570m | 1220m | 440m | 6.72s | 7.40-7.65m |
[Cp2Ti(L3)] | 3000s, 1430m, 1025m | 1610s, 1575m | 1230m | 435m | 6.78s | 7.60-7.78m |
[Cp2Zr(L3)] | 3010s, 1420m, 1030m | 1620s, 1570m | 1225m | 430m | 6.70s | 7.42-7.58m |
[Cp2Ti(L4)] | 2990s, 1415m, 1025m | 1625s, 1585m | 1240m | 440m | 6.75s | 7.60-7.80m 8.20-8.35m |
[Cp2Zr(L4)] | 3000s, 1410m, 1025m | 1610s, 1575m | 1235m | 430m | 6.65s | 7.45-7.70m 8.10-8.25m |
- (a)
- The complexes are slightly more toxic than the parent ligands.
- (b)
- Then titanium complexes show better activity than zirconium complexes.
- (c)
- The best activity was recorded with bis(cyclopentadienyl)titanium (IV) derivatives with ligand L4H2 i.e. derived from 2,6-diaminopyridine.
Compound | Diameter of inhibition zone (mm) | |
---|---|---|
B. Subtilis | E-coli | |
L1H2 [Cp2Ti(L1)] [Cp2Zr(L1)] | 6 14 10 | 8 15 10 |
L2H2 [Cp2Ti(L2)] [Cp2Zr(L2)] | 5 10 8 | 5 10 7 |
L3H2 [Cp2Ti(L3)] [Cp2Zr(L3)] | 12 16 14 | 10 15 12 |
L4H2 [Cp2Ti(L4)] [Cp2Zr(L4)] | 12 16 14 | 12 18 15 |
Ampicillin | 35 | 35 |
Experimental
General
Reactions of Cp2MCl2 (M=Ti or Zr) with ligands
Acknowledgements
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Pandey, O.; Sengupta, S.; Tripathi, C. Reactions of Cp2MCl2 (M=Ti or Zr) with Imine-Oxime Ligands. Formation of Metallacycles. Molecules 2005, 10, 653-658. https://doi.org/10.3390/10060653
Pandey O, Sengupta S, Tripathi C. Reactions of Cp2MCl2 (M=Ti or Zr) with Imine-Oxime Ligands. Formation of Metallacycles. Molecules. 2005; 10(6):653-658. https://doi.org/10.3390/10060653
Chicago/Turabian StylePandey, O., S. Sengupta, and C. Tripathi. 2005. "Reactions of Cp2MCl2 (M=Ti or Zr) with Imine-Oxime Ligands. Formation of Metallacycles" Molecules 10, no. 6: 653-658. https://doi.org/10.3390/10060653