This account summarizes our recent studies on PNP-pincer-type phosphaalkene complexes. Phosphaalkenes with a P=C bond possess an extremely low-lying π* orbital and have a marked tendency to engage in strong π back-bonding with transition metals. This particular ligand property provides PNP-pincer complexes with unique structures and reactivities. 2,6-Bis(phosphaethenyl)pyridine leads to the isolation of coordinatively unsaturated complexes of Fe(I) and Cu(I); the former adopts a trigonal monopyramidal configuration, whereas the latter has a strong affinity for PF6- and SbF6- as non-coordinating anions. Unsymmetrical PNP-pincer-type phosphaalkene complexes of Ir(I) bearing a dearomatized pyridine unit instantly cleave the N-H bond of NH and the C-H bond of MeCN at room temperature. The dearomatized iridium complexes catalyze the dehydrative coupling of amines with alcohols to afford N-alkylated amines and imines in high yields.
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Cu(i) complex bearing a PNP-pincer-type phosphaalkene ligand with a bulky fused-ring Eind group: properties and applications to FLP-type bond activation and catalytic CO reduction.
Dalton Trans
March 2020
National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8565, Japan.
Herein, we report the synthesis of [Cu(Eind2-BPEP)][PF6] (2) (Eind2-BPEP = 2,6-bis(2-Eind-2-phosphaethenyl)pyridine, Eind = 1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6,7-hexahydro-s-indacen-4-yl), a three-coordinated Cu(i) complex bearing a PNP-pincer-type phosphaalkene ligand with bulky fused-ring Eind groups. The Gutmann-Beckett test revealed that complex 2 is highly Lewis acidic and comparable in strength to B(C6F5)3, which is a relatively strong Lewis acid. In addition, 2 is more Lewis acidic than [Cu(Mes*2-BPEP)][PF6] (3), the analogous complex with less-bulky Mes* instead of Eind groups.
View Article and Find Full Text PDFOn the Geometrical Stability of Square-Planar Platinum(0) Complexes That Bear a PNP-Pincer-Type Phosphaalkene Ligand (Eind -BPEP).
Chemistry
November 2018
International Research Center for Elements Science (IRCELS), Institute for Chemical Research & IRCCS, Kyoto University, Uji, Kyoto 611-0011, Japan.
The four-coordinate Pt complex [Pt(PPh )(Eind -BPEP)] (Eind=1,1,3,3,5,5,7,7-octaethyl-1,2,3,5,6,7-hexahydro-s-indacen-4-yl; BPEP=2,6-bis(1-phenyl-2-phosphaethenyl)pyridine), which bears a PNP-pincer-type phosphaalkene ligand (Eind -BPEP; PNP=N,N-bis(diphenylphosphine)-2,6-diaminopyridine), were found to adopt a square-planar configuration around the Pt center (τ =0.11). This coordination geometry is very uncommon for formal d complexes.
View Article and Find Full Text PDFA Square-Planar Complex of Platinum(0).
Angew Chem Int Ed Engl
December 2016
International Research Center for Elements Science (IRCELS), Institute for Chemical Research & IRCCS, Kyoto University, Uji, Kyoto, 611-0011, Japan.
The Pt complex [Pt(PPh )(Eind -BPEP)] with a pyridine-based PNP-pincer-type phosphaalkene ligand (Eind -BPEP) has a highly planar geometry around Pt with ∑(Pt)=358.6°. This coordination geometry is very uncommon for formal d complexes, and the Pd and Ni homologues with the same ligands adopt distorted tetrahedral geometries.
View Article and Find Full Text PDFPNP-Pincer-Type Phosphaalkene Complexes of Late Transition Metals.
Chem Rec
October 2016
Interdisciplinary Research Center for Catalytic Chemistry National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki, 305-8565, Japan.
This account summarizes our recent studies on PNP-pincer-type phosphaalkene complexes. Phosphaalkenes with a P=C bond possess an extremely low-lying π* orbital and have a marked tendency to engage in strong π back-bonding with transition metals. This particular ligand property provides PNP-pincer complexes with unique structures and reactivities.
View Article and Find Full Text PDFReactions of [Cu(X)(BPEP-Ph)] (X = PF6, SbF6) with silyl compounds. Cooperative bond activation involving non-coordinating anions.
Dalton Trans
February 2016
Interdisciplinary Research Center for Catalytic Chemistry, National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki 305-8565, Japan.
Bond activation of silyl compounds, assisted by the cooperative action of non-coordinating anions, is achieved using Cu(I) complexes coordinated with a PNP-pincer type phosphaalkene ligand, [Cu(X)(BPEP-Ph)] (X = PF6 (1a), SbF6 (1b); BPEP-Ph = 2,6-bis[1-phenyl-2-(2,4,6-tri-tert-butylphenyl)-2-phosphaethenyl]pyridine). Complexes 1a and 1b react with Me3SiCN to form Me3SiF and Cu(i) cyanide complexes of the formula [Cu(CN-EF5)(BPEP-Ph)] (E = P (2a), Sb (2b)), in which the CN ligand is associated with the EF5 group arising from EF6(-). Formation of the intermediary isonitrile complex [Cu(CNSiMe3)(BPEP-Ph)](+)SbF6(-) (3b) is confirmed by its isolation.
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