9.
The reaction of [{(η
5-C
5Me
5)M(μ-Cl)Cl}
2] {where M = Rh (1), Ir (
2)} with functionalized phosphine viz., diphenyl-2-pyridylphosphine (PPh
2Py) in dichloromethane solvent yield neutral ϰ
1-P-coordinated rhodium and iridium complexes [(η
5-C
5Me
5)RhCl
2(κ
1-P-PPh
2Py)]
3 and [(η
5-C
5Me
5) IrCl
2(ϰ
1-P-PPh
2Py)]
4. Reaction of complexes 1 and 2 with the ligand PPh
2Py in methanol under reflux give bis-substituted complexes such as [(η
5-C
5Me
5)RhCl(ϰ
1-P-PPh
2Py)
2]
+
5 and [(η
5-C
5Me
5)IrCl(ϰ
1-P-PPh
2Py)
2]
+
6, whereas stirring in methanol at room temperature gives P-, N-chelating complexes of the type [(η
5-C
5Me
5)RhCl(ϰ
2-P-N-PPh
2Py)]
+ 7 and [(η
5-C
5Me
5)IrCl(ϰ
2-P-N-PPh
2Py)]
+
8. Neutral ϰ
1-P-coordinated complexes [(η
5-C
5Me
5)RhCl
2(ϰ
1-P-PPh
2Py)]
3 and [(η
5-C
5Me
5)IrCl
2(ϰ
1-P-PPh
2Py)]
4 easily undergo conversion to the cationic P-, N-chelating complexes [(η
5-C
5Me
5)RhCl(ϰ
2-P-N-PPh
2Py)]
+
7 and [(η
5-C
5Me
5) IrCl(ϰ
2-P, N-PPh
2Py)]
+
8 on stirring in methanol at room temperature. These complexes are characterized by FT-IR and FT-NMR spectroscopy as well as
analytical methods. The molecular structures of the representative complexes [(η
5-C
5Me
5)RhCl
2(ϰ
1-P-PPh
2Py)]
3, [(η
5-C
5Me
5)IrCl
2(ϰ
1-P-PPh
2Py)]
4 and hexafluorophosphate salt of complex [(η
5-C
5Me
5)IrCl(ϰ
2-P-PPh
2Py)
2]
+
6 are established by single-crystal X-ray diffraction methods
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