700346-82-3

Upstream product

• 700346-80-1 Ir₄(CO)8(P(C₆H₅)2(C₆H₄)P(C₆H₅))(P(C₆H₅)2(C₆H₄)) 
• 99685-96-8 fullerene-C₆₀ 
• 19631-23-3 Ir₄(P(C₆H₅)3)3(CO)9 
• 700346-80-1 Ir4(CO)8(μ-κ2-PPh2(o-C6H4)PPh)(μ3-PPh2(η1:η2-o-C6H4)) 

Relevant academic research and scientific papers

Novel [60]fullerene-assisted ortho-phosphanation on a tetrairidium butterfly framework

A mono- to di- and triphosphane transformation occurs on treatment of [Ir4(CO)9(PPh3)3] (1) with C 60 to successively afford 2 and 3. The noninnocent, multifunctional C60 ligand plays a crucial role in transforming three PPh3 ligands into a μ3-PPh2(o-C6H4) P(o-C6H4) PPh(η1-o-C6H 4) triphosphane ligand by a series of ortho-phosphanation and ortho-metalation processes on the Ir4 cluster framework.

Synthetic, electrochemical, and theoretical studies of tetrairidium clusters bearing mono- and bis[60]fullerene ligands

Heating a mixture of lr4(CO)9(PPh3) 3 (1) and 2 equiv of C60 in refluxing chlorobenzene (CB) affords a butterfly tetrairidium-C60 complex lr 4(CO)6{μ3-κ3-PPh 2(o-C6H4)P(o-C6H4) PPh(η1-o-C6H4}}-(μ3- η2:η2-C60) (3, 36%). Brief thermolysis of 1 in refluxing chlorobenzene (CB) gives a butterfly complex lr4(CO)8{μ-k2-PPh2(o-C 6H4)PPh}{μ3-PPh2(η 1:η2-o-C6H4)} (2, 64%) that is both ortho-phosphorylated and ortho-metalated. Interestingly, reaction of 2 with 2 equiv of C60 in refluxing CB produces 3 (41%) by C 60-assisted ortho-phosphorylation, indicating that 2 is the reaction intermediate for the final product 3. On the other hand, reaction of lr 4(CO)8(PMe3)4 (4) with excess (4 equiv) C 60 in refluxing 1,2-dichlorobenzene, followed by treatment with CNCH2Ph at 70 °C, affords a square-planar complex with two C 60 ligands and a face-capping methylidyne ligand, lr 4(CO)3(μ4-CH)(PMe3) 2(μ-PMe2)(CNCH2Ph)(μ-η2: η2-C60)(μ4-η1: η1:η2:η2-C60) (5, 13%) as the major product. Compounds 2, 3, and 5 have been characterized by spectroscopic and microanalytical methods, as well as by single-crystal X-ray diffraction studies. Cyclic voltammetry has been used to examine the electrochemical properties of 2, 3, 5, and a related known butterfly complex lr4(CO)6(μ-CO){μ3-k 2-PPh2(o-C6H4)P(η1-o- C6H4)}(η3-η2: η2:η2-C60) (6). These cyclic voltammetry data suggest that a C60-mediated electron transfer to the iridium cluster center takes place for the species 33- and 6 2- in compounds 3 and 6. The cyclic voltammogram of 5 exhibits six well-separated reversible, one-electron redox waves due to the strong electronic communication between two C60 cages through a tetrairidium metal cluster spacer. The electrochemical properties of 3, 5, and 6 have been rationalized by molecular orbital calculations using density functional theory and by charge distribution studies employing the Mulliken and Hirshfeld population analyses.