TY - JOUR
T1 - Pd(II) Complexes Ligated by 1,3-Bis(diphenylphosphino)calix[4]arene
T2 - Preparation, X-ray Structures, and Catalyses
AU - Hirasawa, Kengo
AU - Tanaka, Shinya
AU - Horiuchi, Takeru
AU - Kobayashi, Takahiro
AU - Sato, Takumi
AU - Morohashi, Naoya
AU - Hattori, Tetsutaro
N1 - Funding Information:
This work was supported in part by a Grant-in-Aid for Scientific Research (C) (no. 15K05466) from the Japan Society for the Promotion of Science (JSPS).
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/2/8
Y1 - 2016/2/8
N2 - syn-1,3-Bis(diphenylphosphino)-2,4-dimethoxycalix[4]arene (7) was synthesized via an Ullmann-type phosphinoylation of the syn-1,3-bis(triflate ester) (2) of p-tert-butylcalix[4]arene, followed by reduction of the phosphinoyl moieties and subsequent methylation of the remaining hydroxy groups. The treatment of diphosphine 7 with 2 molar equiv of PdCl2(MeCN)2 in benzonitrile afforded di-μ-chloro-bridged dinuclear palladium complex 8, formulated as Pd2(7)Cl4, whereas the same reaction conducted in acetonitrile with 1 molar equiv of PdCl2(MeCN)2 yielded mononuclear palladium complex 9, formulated as [Pd(7)Cl(MeCN)]Cl. Complex 9 was transformed into dicationic complex 11, formulated as [Pd(7) MeCN)2](BF4)2, by treatment with AgBF4 in dichloromethane, followed by the addition of acetonitrile. On the other hand, refluxing complex 9 in 1,2-dichloroethane yielded neutral complex 12, formulated as Pd(7)Cl2. In each of the mononuclear complexes, the palladium ion adopts a tetracoordinated square-planar geometry perpendicular to the mean plane defined by the macrocycle, and two phosphorus atoms occupy trans coordination sites. Consequently, an acetonitrile or chlorine ligand coordinates through the cavity of the calixarene, while another acetonitrile or chlorine ligand occupies the exo position. Dicationic complex 11 promoted Suzuki-Miyaura coupling between aryl chlorides and phenylboronic acid and the ring-opening reaction of an epoxide with thiophenol.
AB - syn-1,3-Bis(diphenylphosphino)-2,4-dimethoxycalix[4]arene (7) was synthesized via an Ullmann-type phosphinoylation of the syn-1,3-bis(triflate ester) (2) of p-tert-butylcalix[4]arene, followed by reduction of the phosphinoyl moieties and subsequent methylation of the remaining hydroxy groups. The treatment of diphosphine 7 with 2 molar equiv of PdCl2(MeCN)2 in benzonitrile afforded di-μ-chloro-bridged dinuclear palladium complex 8, formulated as Pd2(7)Cl4, whereas the same reaction conducted in acetonitrile with 1 molar equiv of PdCl2(MeCN)2 yielded mononuclear palladium complex 9, formulated as [Pd(7)Cl(MeCN)]Cl. Complex 9 was transformed into dicationic complex 11, formulated as [Pd(7) MeCN)2](BF4)2, by treatment with AgBF4 in dichloromethane, followed by the addition of acetonitrile. On the other hand, refluxing complex 9 in 1,2-dichloroethane yielded neutral complex 12, formulated as Pd(7)Cl2. In each of the mononuclear complexes, the palladium ion adopts a tetracoordinated square-planar geometry perpendicular to the mean plane defined by the macrocycle, and two phosphorus atoms occupy trans coordination sites. Consequently, an acetonitrile or chlorine ligand coordinates through the cavity of the calixarene, while another acetonitrile or chlorine ligand occupies the exo position. Dicationic complex 11 promoted Suzuki-Miyaura coupling between aryl chlorides and phenylboronic acid and the ring-opening reaction of an epoxide with thiophenol.
UR - http://www.scopus.com/inward/record.url?scp=84957928230&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84957928230&partnerID=8YFLogxK
U2 - 10.1021/acs.organomet.5b00999
DO - 10.1021/acs.organomet.5b00999
M3 - Article
AN - SCOPUS:84957928230
SN - 0276-7333
VL - 35
SP - 420
EP - 427
JO - Organometallics
JF - Organometallics
IS - 3
ER -