Synthesis of the phosphino–fullerene PPh2(o-C6H4)(CH2NMeCH)C60 and its function as an η1-P or η3-P,C2 ligand

Abstract

Following the method of Prato et al., reaction of C₆₀, N-methylglycine and o-(diphenylphosphino)benzaldehyde affords PPh₂(o-C₆H₄)(CH₂NMeCH)C₆₀ (1) in moderate yield. Compound 1 reacts with W(CO)₄(NCMe)₂ to produce W(CO)₄(η³-PPh₂(o-C₆H₄)(CH₂NMeCH)C₆₀) (2), through coordination of the phosphine group and one 6 : 6-ring junction of fullerene. Reaction of 1 and Os₃(CO)₁₁(NCMe) affords Os₃(CO)₁₁(PPh₂(o-C₆H₄)(CH₂NMeCH)C₆₀) (3), which undergoes a cluster fragmentation reaction in refluxing toluene to produce Os(CO)₃(η³-PPh₂(o-C₆H₄)(CH₂NMeCH)C₆₀) (4). Thermal reaction of 1 and Os₃(CO)₁₂ affords 3 and 4. On the other hand, reaction of 1 and Ru₃(CO)₁₂ yields only the mononuclear complex Ru(CO)₃(η³-PPh₂(o-C₆H₄)(CH₂NMeCH)C₆₀) (5). The structures of 1–3 and 5 were determined by an X-ray diffraction study.