Iron and ruthenium derivatives of cyclophosphazenes coordinated through nitrile spacer ligands
1999; Elsevier BV; Volume: 18; Issue: 10 Linguagem: Inglês
10.1016/s0277-5387(99)00009-1
ISSN1873-3719
Autores Tópico(s)Organometallic Complex Synthesis and Catalysis
ResumoN3P3(O–C6H4–tBu)5Cl reacts with 4-hydroxybenzylcyanide in acetone in the presence of K2CO3, to give the cyanide ligand N3P3(O–C6H4–tBu)5(O–C6H4–CH2–CN) (1). The monofunctionalized cyclotriphosphazene, N3P3(O–C6H4–tBu)5(O–C6H4–CH2–CN), reacted with CpFe(dppe)I and with CpRu(PPh3)2Cl in the presence of NH4PF6 and in CH3OH as solvent to give the monocationic complexes [N3P3(O–C6H4–tBu)5(O–C6H4–CH2CN) Fe(Cp)dppe]PF6 (2) and [N3P3(O–C6H4–tBu)5(O–C6H4–CH2–CN)·Ru(Cp)(PPh3)2] PF6 (3), respectively. Electrochemical as well as chemical oxidation of (2) and (3) with NOBF4 yield the stable dicationic species (2)+ and (3)+. Electrochemical as well as spectroscopic data suggest that ligand (1) behaves like a nitrile ligand. The small influence of the cyclophosphazene ring upon coordination is attributed to the long length of the organic spacer groups. An exponential dependence of Δ31Pcoord with the spacer length was found for several organometallic derivatives of cyclophosphazene.
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