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Soon W Lee

Publications and source records attributed to Soon W Lee.

10 recordsLinked to original sources

Bis(isothiocyanato)bis(phosphine) complexes of group 10 metals: reactivity toward organic isocyanides.

Treatment of Ni(NCS)2(PMe2Ph)2 with organic isocyanides CN-R gave five-coordinate isocyanide Ni(II) complexes, Ni(CN-R)(NCS)2(PMe2Ph)2 (R = C6H3-2,6-Me2 (1), t-Bu (2)). Interestingly, the corresponding reaction of Ni(NCS)2(P(n-Pr)3)2 with 2 equiv. of CN-t-Bu gave an unusual compound, which exists as an ion pair of the trigonal bipyramidal cation [Ni(P(n-Pr)3)2(CN-t-Bu)3]2+ (3) and the dinuclear NCS-bridged anion [Ni(1,3-micro-NCS)(NCS)3]2(2-) (4). In contrast, Pd(NCS)2(P(n-Pr)3)2 underwent substitution with 2 equiv. of CN-t-Bu to give the four-coordinate mono(isocyanide) Pd(II) complex Pd(NCS)(SCN)(CN-t-Bu)(P(n-Pr)3) (5) via phosphine dissociation. Reactions of M(NCS)2L2 (M = Pd, Pt; L = PMe3, PEt3, PMePh2, P(n-Pr)3) with two equiv. of CN-R (R = t-Bu, i-Pr, C6H3-2,6-Me2) gave the corresponding bis(isocyanide) complexes [M(CN-R)2(PR3)2](SCN)2 (7-13), except for Pd(NCS)2(PEt3)2 that reacted with CN-R' (R' = i-Pr, C6H3-2,6-Me2) and produced the mono(isocyanide) Pd(II) complexes [Pd(CN-R')(SCN)(PEt3)2](SCN) (14 and 15). Finally, treatment of M(NCS)2(PMe3)2 (M = Ni, Pd, Pt) with sterically bulky isocyanide CN-C6H3-2,6-i-Pr2 gave various products, (16-18) depending on the identity of the metal.

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Indium(III)-induced fluorescent excimer formation and extinction in calix[4]arene-fluoroionophores.

New fluorogenic or/and chromogenic calix[4]arenes 1-3 with two facing amide groups linked to fluorescent pyrene units are synthesized. Orientations of the pyrene units are remote from each other in 1 and face-to-face pi-stacked in 2, which produces different photophysical properties. In the excited state, the two pyrene units of 2 form a strong intramolecular excimer displaying an emission at 472 nm with a relatively weak monomer emission at 395 nm. In contrast, 1 exhibits only a monomer emission at 398 nm because intramolecular hydrogen bonding between the phenolic OH oxygens and the amide hydrogens prevents pi-stacking of the two pyrene groups. Fluorescence changes upon addition of various metal ions show that 1 has a remarkably high selectivity for In(3+) over the other metal ions tested. Compound 1 forms 2:1 (metal:ligand), as well as 1:1 complexes, with In(3+), with fluorescence varying uniquely with the complex stoichiometry. Compound 3, which possess two pyrene units and two chromogenic azo groups, shows almost the same binding behavior toward metal ions as does 1, together with additional bathochromic shifts of the absorption maximum. Compared with 1, compound 3 emits a considerably weaker fluorescence, which is attributed to electron transfer from the pyrene units to the nitro groups of the phenylazo moieties.

Calixarenes↗

Benzene-templated hydrothermal synthesis of metal-organic frameworks with selective sorption properties.

In this paper, we report two metal-organic frameworks [Co3(ndc)3(bipyen)(1.5)]H2O (1) and [Co2(ndc)2bipyen)]C6H6.H2O (2) (bipyen=trans-1,2-bis(4-pyridyl)ethylene, H2ndc=2,6-naphthalenedicarboxylic acid). These compounds were both synthesized from identical hydrothermal reaction conditions except that benzene was added to the reaction for 2. Crystal structures show that the two compounds have triply interpenetrated three-dimensional frameworks and these frameworks have the same primary structure of a two-dimensional network of interconnected [Co2(O2CR)(4/2)] (R=naphthalene group) paddle-wheels and bridging bipyen ligands. Both compounds have guest water molecules and, in addition, 2 has guest benzene molecules. Structural transformations of the host accompanied guest removal, which can be monitored by powder X-ray diffraction. N2 adsorption data of 2 show that there are two different types of pores corresponding to the benzene and water pores. Upon exposure to vapors of several organic molecules, the heat-treated sample of 2 adsorbs benzene and cyclohexene, but does not adsorb toluene, (o-, m-, and p-)xylenes, cycloheptatriene, or cyclohexane.

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Cyclometallated Pd(II) azido complexes containing 6-phenyl-2,2'-bipyridyl or 2-phenylpyridyl derivatives: synthesis and reactivity toward organic isocyanides and isothiocyanates.

Cyclometallated palladium(II) azido complexes containing C,N,N- or C,N-donor ligands, [Pd(N(3))L](HL = 6-phenyl-2,2'-bipyridine or 2-phenylpyridyl derivatives), showed different reactivities toward organic isocyanides and isothiocyanates. In particular, aryl isocyanides (CN-Ar) underwent insertion into the orthometallated Pd-C bond on the phenyl moiety of the supporting ligand (L) in [Pd(N(3))L] or [Pd(N(3))(PR(3))L] to selectively give carbodiimido [[Pd(N=C=N-Ar)L]], imidoyl [[Pd(N(3))(-C=N-Ar)(PR(3))L]], or imidoyl carbodiimido complexes [[Pd(N=C=N-Ar)(-C=N-Ar)L] or [Pd(N=C=N-Ar)(-C=N-Ar)(PR(3))L]], depending on reaction conditions. Interestingly, reactions of [Pd(N(3))(PR(3))L] with organic isothiocyanates gave unusual dinuclear complexes [(micro-SCN(4)-R)PdL](2), exhibiting the concurrent S- and N-coordinating thio-tetrazole bridge.

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Azido- or hydroxyl-capped half-cubanes containing Cp*Rh fragments: [Cp*3Rh3(mu-X)3(mu3-X)]2+ (X-=OH- or N3-).

Treatment of [Cp*Rh(H(2)O)(3)](OTf)(2) (1) with Me(3)SiNH-t-Bu in acetone gave a hydroxyl-capped half-cubane [Cp*(3)Rh(3)(mu-OH)(3)(mu(3)-OH)](OTf)(3)(t-BuNH(3)) (2). Slow diffusion of Me(3)SiN(3) in diethyl ether into compound in acetone produced an azido-capped half-cubane [Cp*(3)Rh(3)(mu-N(3))(3)(mu(3)-N(3))](OTf)(2) (3). On the other hand, treating 1 with Me(3)SiN(3) in acetone gave an azido-bridged, dinuclear rhodium(III) complex [Cp*Rh(mu-N(3))(OH(2))](2)(OTf)(2) (4). Complexes 2 and 3 represent the first azido- or hydroxyl-capped, incomplete cubane-type Rh clusters. Under appropriate conditions, complexes 2 and 3 could be converted to complex 4. The structures of all products were determined by X-ray diffraction.

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Silver ion shuttling in the trimer-mimic thiacalix[4]crown tube.

Novel 1,3-alternate calix-thiacalix[4]crown trimers bearing crown-5 and crown-6 were prepared. As proven by X-ray diffraction, in a 1:2 mole ratio of ligand to metal ion, the Cs(+) and K(+) ions prefer to be encapsulated in the trimeric thiacalix[4]crown-6 and crown-5, respectively. On the contrary, the Ag(+) ion was found to be entrapped in the central thiacalix spacer as a 1:1 complex confirmed by (1)H NMR spectrosocpy. Variable-temperature (1)H NMR studies for the trimeric thiacalix[4]crown-6 encapsulating the silver ion revealed that the Ag(+) ion oscillates through the central thiacalix spacer with the aid of cation-pi interactions.

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Various forms of linear dipyridyls in discrete rectangles, dinuclear rods, and one-dimensional networks containing (eta5-pentamethylcyclopentadienyl)rhodium(III).

[Cp*Rh(eta1-NO3)(eta2-NO3)] (1) reacted with pyrazine (pyz) to give a dinuclear complex [Cp*Rh(eta1-NO3)(mu-pyz)(0.5)]2.CH2Cl2(3.CH2Cl2). Tetranuclear rectangles of the type [Cp*Rh(eta1,mu-X)(mu-L)(0.5)]4(OTf)4(4a: X = N3, L = bpy; 4b: X = N3, L = bpe; 4c: X = NCO, L = bpy) were prepared from [Cp*Rh(H2O)3](OTf)2 (2), a pseudo-halide (Me3SiN3 or Me3SiNCO), and a linear dipyridyl [4,4'-bipyridine (bpy) or trans-1,2-bis(4-pyridyl)ethylene (bpe)] by self-assembly through one-pot synthesis at room temperature. Treating complex with NH4SCN and dipyridyl led to the formation of dinuclear rods, [Cp*Rh(eta1-SCN)3]2(LH2) (5a: L = bpy; 5b: L = bpe), in which two Cp*Rh(eta1-SCN)3 units are connected by the diprotonated dipyridyl (LH2(2+)) through N(+)-H...N hydrogen bonds. Reactions of complex 2 with 1-(trimethylsilyl)imidazole (TMSIm) and dipyridyl (bpy or bpe) also produced another family of dinuclear rods [Cp*Rh(ImH)3]2.L (6a: L = bpy; 6b: L = bpe). Treating 1 and 2 with TMSIm and NH4SCN (in the absence of dipyridyl) generated a 1-D chain [Cp*Rh(ImH)3](NO3)2 (7) and a 1-D helix [Cp*Rh(eta1-SCN)2(eta1-SHCN)].H2O (8.H2O), respectively. The structures of complexes 3.CH2Cl2, 4a.H2O, 4c.2H2O, 5b, 6a, 7 and 8.H2O were determined by X-ray diffraction.

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Azido[1,1'-bis(diphenylphosphino)ferrocene](pentamethylcyclopentadienyl)rhodium(III) hexafluorophosphate.

In the title compound, azido-2kappaN-bis[micro-(1eta(5):2kappaP)-diphenylphosphinocyclopentadienyl][2(eta(5))-pentamethylcyclopentadienyl]iron(III)rhodium(III) hexafluorophosphate, [[Rh(C(10)H(15))(N(3))][Fe(micro-C(17)H(14)P)(2)]]PF(6) or [FeRh(C(10)H(15))(micro-C(17)H(14)P)(2)(N(3))]PF(6), the coordination sphere of Rh(III) can be described as pseudo-tetrahedral, composed of two P atoms from a 1,1'-bis(diphenylphosphino)ferrocene (dppf) ligand, an azido N atom and the centroid of the ring of a C(5)Me(5) (Cp*) ligand. The two cyclopentadienyl rings in the dppf moiety adopt an eclipsed conformation. The Rh.Fe distance is 4.340 (2) A.

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Synthesis and reactivity of 1,2-bis(chlorodimethylgermyl)carborane and 1,2-bis(bromodimethylstannyl)carborane.

The 1,2-bis(chlorogermyl)- (1) and 1,2-bis(bromostannyl)carborane (2) have been prepared by the reaction of dilithio-o-carborane with Me(2)GeCl(2) and Me(2)SnBr(2), respectively. Compounds 1 and 2 are found to be good precursors for the synthesis of a variety of cyclization compounds. The Wurtz-type coupling reaction of 1 and 2 using sodium metal afforded the four-membered digerma compound 3 and five-membered tristanna compound 4, respectively. The salt elimination reactions of 1 and 2 using Li(2)N(t)Bu and Li(2)PC(6)H(5) afforded the cyclic products [structure: see text]. The 1,2-bis(dimethylgermyl)carborane 9 and 1,2-bis(dimethylstannyl)carborane 10 were prepared by the reaction of 1 and 2 with sodium cyanoborohydride. The reactions of 9 and 10 with Pd(PPh(3))(4) afforded the bis(germyl)palladium 12 and bis(stannyl)palladium 13 complexes, respectively.

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