Iridium(I) and Rhodium(I) Cationic Complexes with Triphosphinocalix[6]arene Ligands:  Dynamic Motion with Size-Selective Molecular Encapsulation

Obora, Yasushi; Liu, Yun Kui; Jiang, Li; Takenaka, Kazuhiro; Tokunaga, Makoto; Tsuji, Yasushi

doi:10.1021/om049227j

Cited by 20 publications

(3 citation statements)

References 13 publications

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“…According to the reported synthetic procedure for phosphanylcalix [4]arenes [5n,12] and triphosphanylcalix [6]arenes, [9] 3 was prepared as follows. Reaction of 1 [13] with Ph 2 P(O)CH 2 OTs [14] with NaH as a base, in toluene at 90°C for 2 d, gave the phosphane oxide 2 in 95 % yield.…”

Section: Resultsmentioning

confidence: 99%

“…We recently synthesized 1,3,5-triphosphanylcalix [6]arene, which functions as a tripodal phosphane ligand to afford novel, capsule-shaped Ir I and Rh I complexes. [9] In the present study, we describe the synthesis and characterization of novel phosphanylcalix [6]arenes having mono-O-diphenylphosphanylmethyl (3) and mono-O-(4-diphenylphosphanylphenyl)methyl substituents (5) as the first examples of a calix [6]arene moiety bearing monodentate phosphane ligands. [10] The monodentate phosphanes are an important class of ligands in transition-metal-catalyzed reactions.…”

Section: Introductionmentioning

confidence: 99%

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Monophosphanylcalix[6]arene Ligands: Synthesis Characterization, Complexation, and Their Use in Catalysis

et al. 2005

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Novel phosphanylcalix [6]arenes having mono-O-diphenylphosphanylmethyl (3) and mono-O-(4-diphenylphosphanylphenyl)methyl substituents (5) have been synthesized. The structures of these monophosphanylcalix[6]arenes were determined by NMR spectroscopy, mass spectrometry, and Xray crystal structure analysis. The X-ray structure reveals that 3 adopts a flattened 1,2,3-alternate conformation in the crystalline state, while the NMR spectra show that 3 and 5 have a cone conformation in solution. Structure optimization and energy calculations for 3 and 5 at the B3LYP/LANL2DZ-CONFLEX5/MMFF94s level of theory show that the cone

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Monophosphanylcalix[6]arene Ligands: Synthesis Characterization, Complexation, and Their Use in Catalysis

et al. 2005

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“…These findings illustrate the clear tendency of a-TEPHOS to behave as a strong double chelator towards Rh + , rather than as a bridging ligand as observed for other cavity-shaped polyphosphine ligands. 22 The exact orientation of the P-Rh vectors in 8, away or towards the CD axis, is not known, but the presence of two converging "Rh(NBD)" units appears very likely, as no correlations between the olefinic NBD protons and outer CD protons could be established by ROESY experiments. Note that similarly oriented coordination bonds were found in chelate complexes obtained from CDs substituted either by two adjacent diphenylphosphino or two amino groups.…”

Section: Complexation Properties Of A-tephosmentioning

confidence: 99%

α-TEPHOS: a cyclodextrin-derived tetraphosphine for multiple metal binding

et al. 2007

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The tetraphosphine 6(A),6(B),6(D),6(E)-tetradeoxy-6(A),6(B),6(D),6(E)-tetra(diphenylphosphinyl)-2(A),2(B),2(C),2(D),2(E),2(F),3(A),3(B),3(C),3(D),3(E),3(F),6(C),6(F)-tetradeca-O-methyl-alpha-cyclodextrin (alpha-TEPHOS) has been prepared in high yield by reacting 6(A),6(B),6(D),6(E)-tetra-O-methylsulfonyl-2(A),2(B),2(C),2(D), 2(E),2(F),3(A),3(B),3(C),3(D),3(E),3(F),6(C),6(F)-tetradeca-O-methyl-alpha-cyclodextrin with excess PPh(2)Li. The product was purified in its BH(3)-protected form. alpha-TEPHOS is the first optically active tetraphosphine in which the four phosphine units are tethered to a cavity-shaped scaffold. When reacted with [AuCl(tetrahydrothiophene)], alpha-TEPHOS led to the corresponding tetragold complex [(alpha-TEPHOS)(AuCl)(4)] in which the four gold atoms are all located close to the primary face of the cyclodextrin. Reaction with [PdCl(o-C(6)H(4)CH(2)NMe(2))](2) gave the C(2)-symmetrical complex [(alpha-TEPHOS){PdCl(o-C(6)H(4)CH(2)NMe(2))}(4)]. Treatment of the ligand with two equiv. of [Rh(norbornadiene)(tetrahydrofuran)(2)]BF(4) afforded selectively the bimetallic complex [(alpha-TEPHOS){Rh(norbornadiene)}(2)](BF(4))(2) in which each metal centre is coordinated to two phosphorus atoms belonging to adjacent glucose units.

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