TY - JOUR
T1 - Toward New Organometallic Architectures
T2 - Synthesis of Carbene-Centered Rhodium and Palladium Bisphosphine Complexes. Stability and Reactivity of [PCBImPRh(L)][PF6] Pincers
AU - Plikhta, Andriy
AU - Pöthig, Alexander
AU - Herdtweck, Eberhardt
AU - Rieger, Bernhard
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/9/21
Y1 - 2015/9/21
N2 - In this article, we report the synthesis of a tridentate carbene-centered bisphosphine ligand precursor and its complexes. The developed four-step synthetic strategy of a new PCBImP pincer ligand represents the derivatization of benzimidazole in the first and third positions by (diphenylphosphoryl)methylene synthone, followed by phosphine deprotection and subsequent insertion of a noncoordinating anion. The obtained ligand precursor undergoes complexation, with PdCl2 and [μ-OCH3Rh(COD)]2 smoothly forming the target organometallics [PCBImPPdCl][PF6] and [PCBImPRh(L)][PF6] under mild hydrogenation conditions. A more detailed study of the rhodium complexes [PCBImPRh(L)][PF6] reveals significant thermal stability of the PCBImPRh moiety in the solid state as well as in solution. The chemical behavior of 1,3-bis(diphenylphosphinomethylene)benzimidazol-2-ylrhodium acetonitrile hexafluorophosphate has been screened under decarbonylation, hydrogenation, and hydroboration reaction conditions. Thus, the PCBImPRhI complex is a sufficiently stable compound, with the potential to be applied in catalysis.
AB - In this article, we report the synthesis of a tridentate carbene-centered bisphosphine ligand precursor and its complexes. The developed four-step synthetic strategy of a new PCBImP pincer ligand represents the derivatization of benzimidazole in the first and third positions by (diphenylphosphoryl)methylene synthone, followed by phosphine deprotection and subsequent insertion of a noncoordinating anion. The obtained ligand precursor undergoes complexation, with PdCl2 and [μ-OCH3Rh(COD)]2 smoothly forming the target organometallics [PCBImPPdCl][PF6] and [PCBImPRh(L)][PF6] under mild hydrogenation conditions. A more detailed study of the rhodium complexes [PCBImPRh(L)][PF6] reveals significant thermal stability of the PCBImPRh moiety in the solid state as well as in solution. The chemical behavior of 1,3-bis(diphenylphosphinomethylene)benzimidazol-2-ylrhodium acetonitrile hexafluorophosphate has been screened under decarbonylation, hydrogenation, and hydroboration reaction conditions. Thus, the PCBImPRhI complex is a sufficiently stable compound, with the potential to be applied in catalysis.
UR - http://www.scopus.com/inward/record.url?scp=84942870543&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.5b01428
DO - 10.1021/acs.inorgchem.5b01428
M3 - Article
AN - SCOPUS:84942870543
SN - 0020-1669
VL - 54
SP - 9517
EP - 9528
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 19
ER -