Biomedical subjects
Publications and source records attributed to Wing-Tak Wong.
A convenient synthetic route to 1,4-bis(tert-butoxycarbonylmethyl)tetraazacyclododecane (cyclen) (1) with high yield and excellent regioselectivity is described. Compound 1 reacted with a range of functionalized alkyl halides under two reaction conditions to give mono-N-alkylated 1,4-bis(tert-butoxycarbonylmethyl)tetraazacyclododecane (2-9) in good yield.
Treatment of [Ti(O-i-Pr)(2)Cl(2)] with NaL(OEt) (L(OEt)(-) = [CpCo[P(O)(OEt)(2)](3)](-), Cp = eta(5)-C(5)H(5)) afforded [L(OEt)Ti(O-i-Pr)(2)Cl] that reacted with HCl in ether to give [L(OEt)TiCl(3)] (1). The average Ti-O and Ti-Cl distances in 1 are 1.975 and 2.293 A, respectively. Reaction of titanyl sulfate with NaL(OEt) in water followed by addition of HBF(4) afforded [L(OEt)TiF(3)] (2), the Ti-O and Ti-F distances of which are 2.020(2) and 1.792(2) A, respectively. The Zr(IV) analogue [L(OEt)ZrF(3)] (3) was prepared similarly from zirconyl nitrate, NaL(Oet), and HBF(4) in water. The Zr-O and average Zr-F distances in 3 are 2.139(2) and 1.938(2) A, respectively. Treatment of 1 with tetrachlorocatechol (H(2)Cl(4)cat) afforded [L(OEt)Ti(Cl(4)cat)Cl] (4). The average Ti-O(P), Ti-O(C), and Ti-Cl distances in 4 are 1.972, 1.926, and 2.334 A, respectively. Hydrolysis of 4 in the presence of Et(3)N yielded the mu-oxo dimer [(L(OEt))(2)Ti(2)(Cl(4)cat)(2)(mu-O)] (5). The average Ti-O(P), Ti-O(C), and Ti-O(Ti) distances in 5 are 2.027, 1.926, and 1.7977(9) A. Treatment of 1 with 1,1'-binaphthol (BINOLH(2)) in the presence of Et(3)N afforded [(L(OEt))(2)Ti(2)(mu-O)(2)(mu-BINOL)] x 2BINOLH(2) (6.2BINOLH(2)). Complex 1 is capable of catalyzing ring opening of epoxides with Me(3)SiN(3) under solvent-free conditions presumably via a Ti-azide intermediate.
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A flexible organometallic ligand, 1,1'-ferrocenedicarboxylic acid, was incorporated in the self-assembly of a d-f mixed-metal coordination polymer featuring a 2-D interlinking zigzag-chain network and bearing two kinds of bridging conformations.
The luminescence lifetime of TbL2 with a pendant 15-crown-5 increased by 65% to 2.95 ms with an [Na+] concentration of 0.13 M in aqueous solution; the maximum amplification of the luminescence intensity of TbL1 containing aza-15-crown-5 reached a factor of 47 upon addition of the aromatic antenna p-chlorobenzoate 1.
A series of osmium(VI) nitrido complexes containing Schiff base ligands, [Os(VI)(N)(L)Cl] (L = salophen or salen), have been synthesized by reaction of the ligand with [NBu(n)(4)][Os(VI)(N)Cl(4)] in the presence of 2,6-dimethylpyridine. The nu(Os&tbd1;N) for the salophen complexes occur at around 1070 cm(-)(1) and are insensitive to the nature of the substituents present on the Schiff base ligand. The structures of [Os(N)(salophen)(MeOH)]ClO(4) and [Os(N)(5,5-Cl(2)salophen)(MeOH)]ClO(4) have been determined by X-ray crystallography, and the Os&tbd1;N bond distances are 1.651 and 1.66 Å, respectively. The osmium(VI) nitrido complexes react rapidly with triphenylphosphine to produce the corresponding osmium(IV) phosphoraniminato complexes, [Os(IV)(NPPh(3))(L)Cl]. The osmium(IV) complexes exhibit reversible Os(V/IV) and Os(IV/III) couples in cyclic voltammetry. The E(1/2) values show linear correlations with the Hammett constants sigma(p) of the substituents on the Schiff base ligand. The structure of [Os(IV)(NPPh(3))(salophen)Cl] has been determined by X-ray crystallography. The rather long Os-N(P) bond length (1.92 Å) and acute Os-N-P bond angle (149.6 degrees ) suggest that there is no significant multiple-bond character in the Os-N bond. The kinetics of nitrogen atom transfer from a series of 5,5'-disubstituted salophen nitrido complexes to PPh(3) have been studied in CH(3)CN at 25.0 degrees C by stopped-flow spectrophotometric method. The following rate law was obtained: -d[Os(VI)]/dt = k(2)[Os(VI)][PPh(3)]. The reactivities of the complexes were found to follow a Hammett correlation of log(k(X)/k(H)) with sigma(p), with a rho value of 1.9 +/- 0.1. The positive rho value is consistent with a transition state involving electrophilic attack by the nitrido ligand on the phosphorus atom.
Interaction of Re(N)L(2) [L = N(PSPh(2))(2)] 1 with (CF(3)CO)(2)O or RCOCl afforded air-sensitive acylimido-Re(V) complexes trans-Re[NC(O)CF(3)](OCOCF(3))L(2) 2 or trans-Re[NC(O)R]ClL(2) (R = CCl(2)H 3, CClH(2) 4, CH(3) 5), respectively. Treatment of 1 with (CX(3)CO)(2)O followed by recrystallization from CH(2)Cl(2)/hexane in air led to the formation of the corresponding parent imido complexes trans-Re(NH)(OCOCX(3))L(2) (X = F 6, Cl 7). The structure of 7 has been characterized by X-ray crystallography. The Re-N, average Re-S, and Re-O distances are 1.664(3), 2.441, and 2.116(3) Å, respectively. Deprotonation of 6 or 7 with Et(3)N gave 1. Recrystallization of 3 from CH(2)Cl(2)/hexane in air resulted in oxo-imido exchange and the isolation of the oxo-Re(V) species trans-Re(O)ClL(2). Treatment of 1 with tosyl anhydride gave trans-Re(NH)(OTs)L(2) (OTs = tosyl) 8. Reaction of [n-Bu(4)N][OsNCl(4)] with KL afforded trans-Os(N)ClL(2) 9, which has been characterized by X-ray crystallography. The Os-N, Os-Cl, and average Os-S bond distances in 9 are 1.64(1), 2.577(4), and 2.429 Å, respectively. Treatment of 10 with (CF(3)CO)(2)O, Ag(CF(3)CO(2)), or CF(3)CO(2)H resulted in chloride substitution and the formation of trans-Os(N)(OCOCF(3))L(2) 10. The Os-N, Os-O, and average Os-S distances in 10 are 1.643(5), 2.271(4), and 2.419 Å, respectively. Treatment of 1 with [Ph(3)C]BF(4) resulted in the isolation of trans-Re(NCPh(3))(F)L(2) 11, presumably via the cationic tritylimido intermediate [Re(NCPh(3))L(2)](+). Reaction of 9 with [Ph(3)C]BF(4) led to chloride abstraction and the formation of five-coordinate [Os(N)L(2)]BF(4) 12. The Os-N and average Os-S distances in 12 are 1.646(5) and 2.364 Å, respectively.
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The reaction of Ru(Et(2)dtc)(2)(DMSO)(2) (Et(2)dtc = N,N-diethyldithiocarbamate; DMSO = dimethyl sulfoxide) with t-BuNC gave trans-Ru(Et(2)dtc)(2)(CN-t-Bu)(2), 1. Complex 1 crystallizes in the monoclinic space group P2(1)/n with a = 9.753(2) Å, b = 11.583(2) Å, c = 12.974(2) Å, and beta = 91.8(2) degrees for Z = 2. The crystal structure of 1 shows the trans disposition of the two isocyanides; the mean Ru-S and Ru-C distances are 2.409 and 1.977(2) Å, respectively. Treatment of [Ru(diene)Cl(2)](n)() with Na(Et(2)dtc) afforded Ru(Et(2)dtc)(2)(diene) (diene = bicyclo[2.2.1]hepta-2,5-diene (NBD), 2, 1,5-cyclooctadiene (COD), 3). Complex 2 crystallizes in the triclinic space group P&onemacr; with a = 7.316(1) Å, b = 10.346(1) Å, c = 15.123(2) Å, alpha = 103.69(2) degrees, beta = 93.54(2) degrees, and gamma = 100.61(2) degrees for Z = 2. The mean Ru-S and Ru-C distances in 2 are 2.416 and 2.137 Å, respectively. The reaction of cis-Ru(Et(2)dtc)(2)(CO)(2) with iodine gave the 2:1 molecular iodine complex cis-Ru(Et(2)dtc)(2)(CO)(2).(1)/(2)I(2) 4, which crystallizes in the monoclinic space group P2(1)/c with a = 7.347(2), b = 22.227(2) Å, c = 12.891(2) Å, and beta =95.98 (2) degrees for Z = 4. The mean Ru-S and Ru-C and the I-I distances in complex 4 are 2.427, 1.903, and 2.745(1) Å, respectively. Treatment of Ru(Et(2)dtc)(2)(DMSO)(2) with I(2) gave the linear Ru(II)-Ru(III)-Ru(III) trimer [Ru(3)(Et(2)dtc)(6)(DMSO)(2)](I(3))(2), 5, which crystallizes in the triclinic space group P&onemacr; with a = 14.125(3) Å, b = 20.829(6) Å, c = 13.658(3) Å, alpha = 97.57(2) degrees, beta = 110.01(2) degrees, and gamma = 71.25(2) degrees for Z = 2. The structure of complex 6 can be viewed as consisting of a {Ru(2)(III)(Et(2)dtc)(4)}(2+) core and a {Ru(II)(Et(2)dtc)(2)(DMSO)(2)} moiety, which are linked together via the two dithiocarbamate sulfurs of the latter. While the two Ru(III) centers are connected by a Ru-Ru single bond (Ru-Ru = 2.826(2) Å), there is no direct interaction between the Ru(III) and Ru(II) centers. Oxidation of Ru(Et(2)dtc)(2)L(2) (L = PPh(3), t-BuNC) by I(2) gave the respective [Ru(Et(2)dtc)(2)L(2)](+) cations. The reaction of cis-Ru(Et(2)dtc)(2)(PPh(3))(2) with excess tosyl azide gave the diamagnetic Ru(IV) tetrazene complex Ru(Et(2)dtc)(2)(Ts(2)N(4)), 7. Complex 7 crystallizes in the triclinic space group P&onemacr; with a = 10.380(1) Å, b = 11.322(1) Å, c = 15.310(1) Å, alpha = 106.84(2) degrees, beta = 106.87(2) degrees, and gamma = 92.63(2) degrees for Z = 2. The Ru-S and Ru-N(alpha) distances in 7 are 2.385 and 1.98 Å, respectively. The formal potentials of the Ru dithiocarbamate complexes were determined by cyclic voltammetry.
Treatment of RHgCl (R = Me, Et, Ph, Fc) with the activated cluster [Os(3)(CO)(10)(NCMe)(2)] produces the osmium-mercury mixed-metal clusters [{Os(3)(CO)(10)(&mgr;-Cl)}(2)(&mgr;(4)-Hg)] (1a) and [{Os(3)(CO)(10)(&mgr;-Cl)}(2){&mgr;-HgOs(CO)(4)}(2)] (2a) in low yields. Cluster 1a bears a central wingtip mercury atom simultaneously bridging two {Os(3)(CO)(10)(&mgr;-Cl)} units. Cluster 2a comprises an unprecedented decanuclear osmium-mercury framework in which there is a central linear "Hg-{Os(CO)(4)}(2)-Hg" molecular backbone with the two Os(CO)(4) fragments arranged in a staggered conformation. Cluster 2a is thermally unstable and converts slowly to cis-[Os(CO)(4){(&mgr;-Hg)Os(3)(CO)(10)(&mgr;-Cl)}(2)] (4a) via the extrusion of an Os(CO)(4) moiety under ambient conditions. Cluster 4a comprises two {(&mgr;-Hg)Os(3)(CO)(10)(&mgr;-Cl)} subcluster units bonded to a central Os(CO)(4) moiety in a cis configuration. Similar reactions with PhHgBr and MeHgI have also been investigated. Cluster 1a crystallizes in the triclinic space group P&onemacr; with a = 9.112(2) Å, b = 12.314(2) Å, c = 15.501(4) Å, alpha = 84.92(2), degrees beta = 88.26(3), degrees gamma = 79.52(2) degrees and Z = 2. Cluster 2a crystallizes in the triclinic space group P&onemacr; with a = 13.306(2) Å, b = 20.768(5) Å, c = 9.771(4) Å, alpha = 96.36(3), degrees beta = 90.50(2), degrees gamma = 98.81(2) degrees and Z = 2. Cluster 4a crystallizes in the triclinic space group P&onemacr; with a = 18.356(2) Å, b = 19.100(3) Å, c = 14.478(2) Å, alpha = 89.783(2), degrees beta = 113.19(2), degrees gamma = 113.70(2) degrees and Z = 4.
A bis-hydrated Gd3+ complex based on tris acetic acid-1,4,7,10-tetraazacyclododecane (DO3A) that was functionalized with aza-15-crown-5 demonstrated a nearly optimal water-exchanging rate (k(ex) = 3.1 x 10(7) s(-1)) and low acute cytotoxicity. Efficient magnetic resonance signal intensity enhancements and prolonged residence lifetime induced by this small molecular complex in vivo were demonstrated even with one-fifth of the standard dosage used in the clinic.