%0 Generic %A Dubs, Christian %A Yamamoto, Toshiki %A Inagaki, Akiko %A Akita, Munetaka %D 2006 %T Synthesis of a Library of Iridium-Containing Dinuclear Complexes with Bridging PNNN and PNNP Ligands (BL), [LM(μ-BL)M‘L‘]BF4. 2. Preparation, Basic Coordination Properties, and Reactivity of the Carbonyl Complexes %U https://acs.figshare.com/articles/dataset/Synthesis_of_a_Library_of_Iridium_Containing_Dinuclear_Complexes_with_Bridging_PNNN_and_PNNP_Ligands_BL_LM_BL_M_L_BF_sub_4_sub_2_Preparation_Basic_Coordination_Properties_and_Reactivity_of_the_Carbonyl_Complexes/3233806 %R 10.1021/om050897e.s002 %2 https://acs.figshare.com/ndownloader/files/5067871 %K BL %K dinuclear carbonyl complexes %K ligand %K acetylide complexes %K PNNP %K PNNN %K dinuclear PNNX complexes catalyze alkyne hydrogenation %K allyl alcohol %K CO %K Basic Coordination Properties %K LM %X 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-η12-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. %I ACS Publications