%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-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.
%I ACS Publications