881913-75-3Relevant academic research and scientific papers
Synthesis of a library of iridium-containing dinuclear complexes with bridging PNNN and PNNP ligands (BL), [LM(μ-BL)M′L′]BF 4. 2. Preparation, basic coordination properties, and reactivity of the carbonyl complexes
Dubs, Christian,Yamamoto, Toshiki,Inagaki, Akiko,Akita, Munetaka
, p. 1359 - 1367 (2008/10/09)
A series of dinuclear carbonyl complexes with PNNP and PNNN ligands, [(L)M(PNNX)M′(L)]BF4 (X = P, N; M(L), M′(L′) = Ir(CO)2, Rh(CO)2, Pd(allyl)), have been prepared by carbonylation (1 atm) of the corresponding cod complexes, and the Rh/Ir complexes have been further converted to μ-η1: η2-acetylide complexes, where effective π-back-donation to the acetylide ligand is essential to stabilize them. On the basis of the stability of the acetylide complexes, the π-donating ability of the metal fragment in the PNNX system is estimated to be (P,N)Rh > (P,N)Ir > (N,N)M. The dinuclear PNNX complexes catalyze alkyne hydrogenation, alkene hydroformylation, and allylation of aniline with allyl alcohol, and, for the allylation, a dinuclear mechanism involving activation of allyl alcohol by interaction with a CO ligand is proposed.
