Search PubMed⌕ Search

SEARCH · Search PubMed

Results for “macrocycles”

Search indexed PubMed citations on genomics, clinical trials, systematic reviews and public health. Explore titles, authors and supplied subject terms, then open the PubMed record.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 829 records · Page 46Linked to original sources
PubMed1996

Formation and X-ray Structures of PCP Ligand Based Platinum(II) and Palladium(II) Macrocycles.

The coordination behavior prior to C-M bond formation of the chelating aromatic PCP substrate DPPMH (3; DPPMH = 1,3-bis((diphenylphosphino)methylene)mesitylene) has been studied in order to determine the factors which control the complex formation of such ligands. Reacting 3 with (RCN)(2)MCl(2) (R = Me, Ph; M = Pd, Pt) and (COD)PtX(2) (X = Cl, Me; COD = 1,5-cyclooctadiene) resulted in the formation of several 8- and 16-membered mono- and binuclear palladium(II) and platinum(II) macrocycles: trans-[(DPPMH)PdCl(2)](2) (5), trans-[(DPPMH)PtCl(2)](2) (6), cis-(DPPMH)PtCl(2) (7), cis-(DPPMH)PtMe(2) (8), and cis-[(DPPMH)PtMe(2)](2) (9). Compounds 5-9 were fully characterized using NMR, FAB-MS, FD-MS, elemental analysis, and X-ray crystallography. Thermolysis of the bimetallic trans-[(DPPMH)PtCl(2)](2) (6) results in the formation of the monomeric cis-(DPPMH)PtCl(2) (7). The product formation depends on the neutral- (nitriles or COD) and anionic ligands (Cl and CH(3)) of the metal precursor. The molecular structures of trans-[(DPPMH)PdCl(2)](2) (5) and cis-[(DPPMH)PtMe(2)](2) (9) have been determined by complete single-crystal diffraction studies. Crystal data for 5: monoclinic, space group P2(1)/n with a = 14.547(3) Å, b = 17.431(4) Å, c = 27.839 (5) Å, beta = 99.56(2) degrees, V = 6961(3) Å(3), and Z = 4. The structure converged to R = 0.048 and R(w) = 0.049. Crystal data for 9: monoclinic, space group P2(1)/n with a = 19.187(4) Å, b = 19.189(4) Å c = 20.705(2) Å, beta = 103.41(3) degrees, V = 7415(3) Å(3), and Z = 4. The structure refinement converged to R = 0.0977 and R(w) = 0.2212.

Journal Article↗
PubMed1996

CO(2) Fixation by Novel Copper(II) and Zinc(II) Macrocyclic Complexes. A Solution and Solid State Study.

Solutions containing Zn(II) and Cu(II) complexes with [15]aneN(3)O(2) rapidly adsorb atmospheric CO(2) to give {[ZnL](3)(&mgr;(3)-CO(3))}.(ClO(4))(4) (2) and {[CuL](3)(&mgr;(3)-CO(3))}.(ClO(4))(4) (4) complexes. The crystal structures of both complexes have been solved (for 2, space group R3c, a, b = 22.300(5) Å, c = 17.980(8) Å, V = 7743(4) Å(3), Z = 6, R = 0.0666, R(w)(2) = 0.1719; for 4, space group R3c, a, b = 22.292(7) Å, c = 10.096(8) Å, V = 7788(5) Å(3), Z = 6, R = 0.0598, R(w)(2) = 0.1611), and the spectromagnetic behavior of 4 has been studied. In both compounds a carbonate anion triply bridges three metal cations. Each metal is coordinated by one oxygen of the carbonate, three nitrogens, and an oxygen of the macrocycle; the latter donor weakly interacts with the metals. Although the two compounds are isomorphous, they are not isostructural, because the coordination geometries of Zn(II) in 2 and Cu(II) in 4 are different. The mixed complex {[CuZn(2)L(3)](&mgr;(3)-CO(3))}.(ClO(4))(4) has been synthesized. X-ray analysis (space group R3c, a, b = 22.323(7) Å, c = 17.989(9) Å, V = 7763(5) Å(3), Z = 6, R = 0.0477, R(w)(2) = 0.1371) and EPR measurements are in accord with a &mgr;(3)-carbonate bridging one Cu(II) and two Zn(II) ions in {[CuZn(2)L(3)](&mgr;(3)-CO(3))}(4+). Both the Zn(II) and Cu(II) cations exhibit the same coordination sphere, almost equal to that found in the trinuclear Zn(II) complex 2. The systems Zn(II)/L and Cu(II)/Lhave been studied by means of potentiometric measurements in 0.15 mol dm(-)(1) NaCl and in 0.1 mol dm(-)(3) NaClO(4) aqueous solutions; the species present in solution and their stability constants have been determined. In both systems [ML](2+) species and hydroxo complexes [M(II)LOH](+) (M = Zn, Cu) are present in solution. In the case of Cu(II), a [CuL(OH)(2)] complex is also found. The process of CO(2) fixation is due to the presence of such hydroxo-species, which can act as nucleophiles toward CO(2). In order to test the nucleophilic ability of the Zn(II) complexes, the kinetics of the promoted hydrolysis of p-nitrophenyl acetate has been studied. The [ZnLOH](+) complex promotes such a reaction, where the Zn(II)-bound OH(-) acts as a nucleophile to the carbonyl carbon. The equilibrium constants for the addition of HCO(3)(-) and CO(3)(2)(-) to the [ZnL](2+) complex have been potentiometrically determined. Only [ML(HCO(3))](+) and [ML(CO(3))] species are found in aqueous solution. A mechanism for the formation of {[ML](3)(&mgr;(3)-CO(3))}.(ClO(4))(4) is suggested.

Journal Article↗
PubMed1996

Carboracycles: Macrocyclic Compounds Composed of Carborane Icosahedra Linked by Organic Bridging Groups.

A family of macrocyclic compounds are described, together with their precursors. These cycles are composed of icosahedral carboranes linked via their carbon vertices through 1,3-trimethylene, alpha,alpha'-1,3-xylylene, or alpha,alpha'-2,6-lutidylene groups. The compounds cyclo-(1,3-trimethylene-1',2'-closo-1',2'-C(2)B(10)H(10))(4) (6a), cyclo-(1,3-trimethylene-1',2'-closo-9',12'-dimethyl-1',2'-C(2)B(10)H(8))(4) (6b), cyclo-(1,3-trimethylene-1',2'-closo-1',2'-C(2)B(10)H(10))(3) (9), cyclo-(alpha,alpha'-1,3-xylylene-1',2'-closo-1',2'-C(2)B(10)H(10))(2) (11a), cyclo-(alpha,alpha'-1,3-xylylene-1',7'-closo-1',7'-C(2)B(10)H(10))(2) (11b), cyclo-(alpha,alpha'-1,3-xylylene-1',7'-closo-9',10'-dimethyl-1,7-C(2)B(10)H(8))(2) (11c), cyclo-(alpha,alpha'-1,3-xylylene-1',2'-closo-1',2'-C(2)B(10)H(10))(4) (12), cyclo-(alpha,alpha'-1,3-xylylene-1',7'-closo-1',7'-C(2)B(10)H(10))(3) (13), cyclo-(alpha,alpha'-2,6-lutidylene-1',7'-closo-1',7'-C(2)B(10)H(10))(2) (19), and cyclo-(alpha,alpha'-2,6-lutidylene N-oxide-1',7'-closo-1',7'-C(2)B(10)H(10))(2) (20) have been synthesized. The structures of 6a, 6b, 9, 11a, 11b, 11c, 12, and 19 have been determined by X-ray crystallography. Crystal data: for 6a, triclinic, space group P&onemacr;, a = 11.131(2) Å, b = 12.642(2) Å, c = 12.996(2) Å, alpha = 84.383(6) degrees, beta = 65.884(6) degrees, gamma = 97.292(5) degrees, Z = 1, R = 0.079; for 6b, monoclinic, space group P2(1)/a, a = 13.500(2) Å, b = 31.141(3) Å, c = 13.831(2) Å, beta = 99.90(1) degrees, Z = 2, R = 0.097; for 11a, monoclinic, space group C2/c, a = 14.5682(8) Å, b = 14.5046(8) Å, c = 16.1998(8) Å, beta = 95.631(2) degrees, Z = 4, R = 0.081; for 11b, monoclinic, space group P2(1)/n, a = 11.650(2) Å, b = 10.606(2) Å, c = 11.730(2) Å, beta = 104.951(6) degrees, Z = 2, R = 0.069; for 11c, orthorhombic, space group Pbca, a = 12.532(2) Å, b = 14.271(2) Å, c = 18.143(3) Å, Z = 4, R = 0.076; for 19, orthorhombic, space group Pcab (No. 61, standard setting Pbca), a = 11.0428(6) Å, b = 11.3785(6) Å, c = 22.533(1) Å, Z = 4, R = 0.074.

Journal Article↗
PubMed1996

Host-Guest Interactions of Inorganic Phosphates with the Copper(II) Complexes of the Hexaaza Macrocyclic Ligand 3,6,9,17,20,23-Hexaazatricyclo[23.3.1.1(11,15)]triaconta-1(29),11(30),12,14,25,27-hexaene.

The host-guest interactions between ortho-, pyro-, and tripolyphosphate anions and the mono and dinuclear copper(II) complexes of the hexaaza macrocyclic ligand BMXD (3,6,9,17,20,23-hexaazatricyclo[23.3.1.1(11,15)]triaconta-1(29),11(30),12,14,25,27-hexaene) were investigated by potentiometric equilibrium methods. Ternary complexes are formed in aqueous solution as a result of coordinate bonding, hydrogen bond formation, and Coulombic attraction between the host and guest. Formation constants for all the species found are reported. The dinuclear copper(II) complexes of BMXD show strong selectivity for pyrophosphate ions in the presence of orthophosphate ions over the whole p[H] range; the pyrophosphate/tripolyphosphate selectivity is p[H] dependent. The dinuclear copper(II) complex of BMXD, (Cu(2)-BMXD)(SO(4))(2), crystallizes in the orthorhombic space group Pccn, with a = 15.73(2) Å, b = 20.27(1) Å, c = 9.045(5) Å, and Z = 4. The sulfate counterions are found to bridge the copper(II) ions in adjacent molecules leading to an extended polymeric structure.

Journal Article↗
PubMed1997

Migratory Transmetalation in Diphenoxo-Bridged Cu(II)M(II) Complexes of a Dinucleating Macrocycle with N(amine)(2)O(2) and N(imine)(2)O(2) Metal-Binding Sites.

A phenol-based heterodinucleating macrocycle (H(2)L), comprised of two 2-((methylamino)methyl)-6-(iminomethyl)-4-bromophenolate entities bridged by the -(CH(2))(2)- groups between amine nitrogens and by the -(CH(2))(3)- groups between imine nitrogens, displays dissimilar N(amine)(2)O(2) and N(imine)(2)O(2) metal-binding sites sharing the phenolic oxygens and is prepared as a Cu(II)Pb(II) complex [CuPb(L)](ClO(4))(2). An analogous complex [CuPb(L)(BzO)(dmf)]ClO(4) crystallizes in the triclinic space group P&onemacr;, (No. 2), with a = 13.998(2) Å, b = 15.568(2) Å, c = 8.699(2) Å, alpha = 95.32(1) degrees, beta = 92.23(1) degrees, gamma = 82.81(1) degrees, V = 1871.9(5) Å(3), and Z = 2. Refinements based on 3788 reflections with I > 3.00sigma(I) converged with R = 0.058 and R(w) = 0.069. The Cu(II) resides at the N(imine)(2)O(2) site and assumes a planar geometry. The Pb(II) resides at the N(amine)(2)O(2) site and assumes a seven-coordinate geometry by further addition of a dmf molecule and a bidentate benzoate group. The Cu--Pb separation, doubly bridged by the phenolic oxygens, is 3.466(2) Å. The reaction of [CuPb(L)](ClO(4))(2) with metal(II) sulfate salts provides Cu(II)M(II) complexes [CuM(L)](ClO(4))(2).nH(2)O (M = Mn (n = 2), Co (n = 2), Ni (n = 0), Cu (n = 0), Zn (n = 1)). The CuZn complex, [CuZn(L)(AcO)]ClO(4), crystallizes in the triclinic space group P&onemacr;, (No. 2), with a = 12.290(3) Å, b = 13.402(4) Å, c = 11.501(2) Å, alpha = 95.10(2) degrees, beta = 116.68(2) degrees, gamma = 112.00(2) degrees, V = 1491.8(9) Å(3), and Z = 2. Refinements based on 2497 reflections with I > 3.00sigma(I) converge with R = 0.046 and R(w) = 0.034. The Cu(II) is bound at the N(amine)(2)O(2) site and the Zn(II) is bound at the N(imine)(2)O(2) site with a Cu--Zn separation of 2.942(2) Å. Further, the acetate group bridges the two metal ions providing a five-coordinate geometry about both metal ions. The CuM complexes except for the CuZn complex show significant antiferromagnetic spin-exchange within each dinuclear unit. The CuNi complex shows the ESR spectrum of the spin-doublet ground state which demonstrates the delocalization of the unpaired electron over the CuNi core.

Journal Article↗
PubMed1998

Synthesis and Reactivity of Nickel(II) Complexes of the Pyridine-Based Phosphorus-Containing Macrocycle 6-Phenyl-15-aza-6-phospha-3,9- dithiabicyclo[9,3,1]pentadeca-1(15),11,13-triene.

The reactivity of the phosphomacrocycle 6-phenyl-15-aza-6-phospha-3,9-dithiabicyclo[9,3,1]pentadeca-1(15), 11,13-triene (L) toward different Ni(II) salts has been studied. The reaction of L with 1 molar equiv of Ni(II) perchlorate in acetonitrile solution gives the complex [Ni(L)(CH(3)CN)(2)](ClO(4))(2) (1), which crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 12.704(2) Å, b = 13.538(2) Å, c = 17.377(2) Å, beta = 107.554(8) degrees, and Z = 4. The Ni(II) atom in 1 shows an octahedral environment defined by the four donor atoms of L and two acetonitrile molecules in a cis disposition. The reaction of L with Ni(II) perchlorate in 2:1 molar ratio yields the green complex [Ni(Lox)(2)](ClO(4))(2) (2) in which the phosphine groups of the ligand L are in their phosphine-oxide form (Lox). The same complex is also obtained by adding more ligand L to an acetonitrile solution of 1. Complex 2 crystallizes in the triclinic space group P&onemacr; (No. 2) with a = 10.564(1) Å, b = 11.975(2) Å, c = 9.124(2) Å, alpha = 109.79(1) degrees, beta = 95.67(2) degrees, gamma = 109.19(1) degrees, and Z = 1. The octahedral coordinated Ni(II) atom in 2 lies on a crystallographic center of symmetry, and it is surrounded by two pyridine nitrogen atoms, two thioether sulfur atoms, and two phosphine-oxide oxygen atoms provided by two facially coordinated Lox ligands. The reaction of L with Ni(II) chloride and Ni(II) thiocyanate yields the complexes [NiCl(2)(L)] (3) and [Ni(NCS)(2)(L)] (4), respectively, which are also obtained by adding Me(4)NCl or KSCN to an acetonitrile solution of 1. Complex 4 crystallizes in the monoclinic space group P2(1)/n (No. 14), with a = 11.139(2) Å, b = 13.270(2) Å, c = 14.885(1) Å, beta = 92.34(1) degrees, and Z = 4, and its structure is similar to that of complex 1, simply replacing the two acetonitrile molecules by two SCN(-) anions. The reactions of the complex 1 with different chelating (en, bipy, o-phen) and nonchelating (py) N-donor ligands have also been carried out. In all cases the two acetonitrile molecules of 1 are easly replaced by the N-donor ligands, but the macrocycle L molecule remains coordinated to the Ni(II) atom. The crystal structure of the complex [Ni(L)(py)(2)](ClO(4))(2) (5) is also elucidated. Crystal data: monoclinic space group P2(1)/c (No. 14) a = 13.063(2) Å, b = 16.615(3) Å, c = 14.973(3) Å, beta = 91.76(2) degrees, Z = 4.

Journal Article↗
PubMed1998

Synthesis and Characterization of [Mn(III)(6)(N-formylsalicylhydrazidate)(6)(MeOH)(6)]: A New Type of Macrocyclic Hexanuclear Manganese Cluster.

The macrocyclic hexanuclear metal cluster, [Mn(III)(6)(fshz)(6)S(6)], 1 (S = MeOH), was prepared using a trianionic pentadentate ligand, N-formylsalicylhydrazidate (fshz(3)(-)). Due to the meridional coordination of the ligand to the metal ion, the ligand is not only bridging the ring metal ions using a hydrazide N-N group but also enforcing the stereochemistry of the metal ions as a propeller configuration. The alternations of the chiralities of the metal centers expand the cyclic ring system of complex 1 to the 24-membered ring system. The neutral hexanuclear manganese complex with noncrystallographic pseudo-C(3)(i)() symmetry is in the crystallographic inversion center. The disc-shaped hexanuclear cluster is 1.8 nm in diameter and 0.8 nm in thickness and has a vacant cavity in the center of the cluster. Three solvent molecules coordinated at the metal centers with Lambda configuration are in one face of the cluster, and the remaining three solvent molecules coordinated at the other metal centers with Delta configuration are in the other face of the cluster. The two faces of the cluster have opposite chiralities to each other. The crystal packing structure of complex 1 shows that the disc-shaped hexanuclear clusters are aligned approximately along the crystallographic a axis. The cavities of the clusters in the crystal structure are also aligned, and one-dimensional channels are formed. The solution integrity of the cluster was addressed using solution mass spectrometry, paramagnetically shifted (1)H NMR spectroscopy, and UV-visible spectroscopy. Crystallographic data for 1: triclinic, P&onemacr;, a = 10.0237(9) Å, b = 15.096(1) Å, c = 15.617(1) Å, alpha = 112.142(5) degrees, beta = 106.615(5) degrees, gamma = 99.958(7) degrees, V = 1989.8(3) Å(3), Z = 2, D(calcd) = 1.510 g cm(-)(1), R1 = 0.0502 and wR2 = 0.1424 for 4249 reflections with I > 2sigma(I), GOF = 1.065.

Journal Article↗
PubMed1998

Structural, EPR, and Electrochemical Studies of Binuclear Copper(II) Complexes of Bis(pentadentate) Ligands Derived from Bis(1,4,7-triazacyclonane) Macrocycles.

Structural, electrochemical, and EPR studies of binuclear copper(II) complexes of bis(pentadentate) ligands, obtained by attaching 2-pyridylmethyl arms to the four secondary nitrogens of bis(tacn) macrocycles linked by ethyl (tmpdtne, [Cu(2)(tmpdtne)](ClO(4))(4).2H(2)O 2), propyl (tmpdtnp, [Cu(2)(tmpdtnp)](ClO(4))(4) 3), butyl (tmpdtnb, [Cu(2)(tmpdtnb)](ClO(4))(4) 4), m-xylyl (tmpdtnm-X, [Cu(2)(tmpdtnm-X)](ClO(4))(4).2DMSO.2H(2)O, 5), and 2-propanol (tmpdtnp-OH, [Cu(2)(tmpdtnp-OH)](ClO(4))(4).2H(2)O, 6) bridges, are reported, together with further analysis of the mononuclear complex, [Cu(dmptacn)](ClO(4))(2) 1, dmptacn = 1,4-bis(2-pyridylmethyl)-1,4,7-triazacyclononane. Single-crystal X-ray diffraction studies established the molecular structure of 3 and the tetrakis(DMF) solvate of 4. Complex 3 crystallizes in the monoclinic space group P2(1)/c (No. 14) with a = 13.867(3), b = 13.548(6), c = 28.055(4) Å, beta = 102.63(1) degrees, V= 5143(2) Å(3), and Z = 4. Refinement gave R = 0.085 and R(w) = 0.089 for 3696 observed reflections. 4 crystallizes in the triclinic space group &Pmacr; (No. 2) with a = 11.775(4), b = 12.718(3), c = 13.201(3) Å, alpha = 61.25(2), beta = 75.99(3), gamma = 77.66(3) degrees, V = 1673(1) Å(3), and Z = 1. Refinement gave R = 0.072 and R(w) = 0.065 for 3876 observed reflections. In 4, the pentadentate compartments are oriented in an anti configuration, while in 3, constraints introduced by the propane bridging group result in a syn configuration. Both complexes exhibit distorted square pyramidal (SP) geometries about the Cu(II) centers with Cu-N(apical) approximately 2.25 Å and Cu-N(equatorial) approximately 2.0 Å. Molecular mechanics calculations have been carried out on these types of complexes for the first time in order to predict the solution structures of 5 and 6. The calculations revealed that the SP geometry is also preferred by these complexes and that there is little energy difference between the syn and anti configurations. Cyclic, square-wave, and steady-state voltammetric studies on 1-6 indicate that, on the time scale of the measurements, 1 undergoes a one-electron reduction to the Cu(I) state while 2-6 undergo an overall two-electron reduction to the binuclear Cu(I) complexes. For 2-4, a shift in reduction potential to more negative values with increasing Cu.Cu separation reflects the stabilization of the Cu(II) state while the two partially resolved reduction processes for 6 suggest that the alcohol group in the ligand backbone promotes a small level of interaction between copper centers.

Journal Article↗
PubMed1999

Synthesis, X-ray Structure, and Solution NMR Studies of Ln(III) Complexes with a Macrocyclic Asymmetric Compartmental Schiff Base. Preference of the Ln(III) Ions for a Crown-Like Coordination Site.

The compartmental ligand H(2)L(A), containing an N(3)O(2) Schiff base and an O(2)O(3) crown like coordination site, has been prepared by reaction of 3,3'-(3-oxapentane-1,5-diyldioxy)bis(2-hydroxybenzaldehyde) with 1,5-diamino-3-azamethylpentane. The formation of a [1+1] macrocycle was inferred by IR, NMR, and mass spectrometry. When reacted with the rare-earth hydrate chlorides, LnCl(3).nH(2)O (Ln = La, Ce, Pr, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y), H(2)L(A) or its precursors (template reaction) form the mononuclear complexes [Ln(H(2)L(A))(H(2)O)(4)]Cl(3).nH(2)O where the lanthanide ion coordinates the O(2)O(3) crown like site. The solid-state X-ray structures of [Ln(H(2)L(A))(H(2)O)(4)]Cl(3).nH(2)O (Ln = Ce, Dy, Lu) have been determined. [Lu(H(2)L(A))(H(2)O)(4)]Cl(3).3H(2)O is monoclinic space group P2(1)/n (Z = 4) with a = 15.269(5) Å, b = 11.484(5) Å, c = 19.389(6) Å, beta = 102.85(5) degrees; [Ce(H(2)L(A))(H(2)O)(4)]Cl(3).H(2)O and [Dy(H(2)L(A))(H(2)O)(4)]Cl(3).H(2)O are isomorphous, space group P2(1) (Z = 2), with a = 10.959(5) Å, b = 16.978(5) Å, c = 9.017(4) Å, beta = 97.73(5) degrees, and a = 10.874(5) Å, b = 16.797(5) Å, c = 9.046(4) Å, beta = 97.86(5) degrees for the cerium and dysprosium complexes, respectively. In the three compounds the metal ion is coordinated in a similar manner by the five oxygens (two phenolic and three etheric) of the cyclic ligand and the nine coordination around the central atom is reached by the oxygen atoms of four coordinated water molecules. Three chlorine ions are present in the asymmetric unit. A detailed (1)H NMR study was carried out in CD(3)OD for both the diamagnetic and paramagnetic [Ln(H(2)L(A))(H(2)O)(4)]Cl(3) complexes in order to compare their structure in solution with that found in the solid state. The quantitative analysis of the paramagnetic proton shifts indicates that the complexes from La to Tm are isostructural, maintain in solution the same type of coordination polyhedron found at the solid state, with the metal ion invariably coordinated in the O(2)O(3) compartment, and present a high degree of stereochemical nonrigidity. In the case of the Lu complex, the decreased fluxionality due to the reduced ionic radius allows the observation of two isomeric species in the (1)H NMR spectrum at low temperature.

Journal Article↗
PubMed1999

Copper(I) Complexes with a NS(2)-Macrocyclic Ligand Bearing a Pendant Naphthyl Group: Structures of {N-[2-(1-Naphthyl)ethyl]-1-aza-4,8-dithiacyclodecane}copper(I)-Ligand, where Ligand = eta(2)-Naphthalene, Acetonitrile, or Triphenylphosphine.

A new macrocyclic ligand with a pendant naphthalene group, N-[2-(1-naphthyl)ethyl]-1-aza-4,8-dithiacyclodecane (L), has been synthesized and characterized. The copper(I)-acetonitrile complex [LCu(CH(3)CN)](PF(6)) (1) was synthesized from L and [Cu(CH(3)CN)(4)](PF(6)). The acetonitrile ligand from 1 was easily removed to give [LCu](PF(6)) (2). Complexes 1 and 2 have been crystallographically characterized. 1: C(21)H(28)N(2)CuF(6)PS(2), triclinic, P&onemacr;, a = 11.1901(10) Å, b = 11.2735(12) Å, c = 12.1350(10) Å, alpha = 98.996(8) degrees, beta = 117.188(6) degrees, gamma = 105.354(7) degrees, Z = 2, R1 = 0.0505 (wR2 = 0.1418). 2.0.5hexane: C(22)H(31)NCuF(6)PS(2), monoclinic, P2(1)/c, a = 15.7318(15) Å, b = 8.9164(10) Å, c = 17.205(5) Å, beta = 102.431(6) degrees, Z = 4, R1 = 0.0587 (wR2 = 0.1545). In addition, a cocrystallized mixture of both complexes was crystallographically characterized. 1&2.hexane: C(46)H(61)N(3)Cu(2)F(12)P(2)S(4), triclinic, P&onemacr;, a = 10.8308(9) Å, b = 12.6320(8) Å, c = 19.9412(13) Å, alpha = 80.445(5) degrees, beta = 76.405(6) degrees, gamma = 78.825(5) degrees, Z = 2, R1 = 0.0661 (wR2 = 0.1871). The solid-state structure of 2 features the pendant naphthalene group bound in an eta(2)-fashion, which is highly unusual for copper complexes. In CDCl(3), 2 exhibits fluxional behavior with the barrier to the process estimated, DeltaG() = 12-13 kcal. Variable temperature NMR spectroscopy gave compelling evidence for solution binding of the naphthalene group in 2, apparently the first example for copper(I). The fluxional process seen for 1 is best described as interconversion of the two enantiomers via a species with an unbound naphthalene group. Consistent with the weak binding of the naphthalene group, it is readily replaced with other ligands, such as triphenylphosphine to form [LCu(PPh(3))](PF(6)) (3). Complex 3 has also been structurally characterized: C(37)H(40)NCuF(6)P(2)S(2), monoclinic, P2(1)/c, a = 11.462(2) Å, b = 15.972(2) Å, c = 19.835(9) Å, beta = 94.50(3) degrees, Z = 4, R1 = 0.0906 (wR2 = 0.1889).

Journal Article↗
PubMed1999

Electrochemistry of Macrocyclic Cobalt(III/II) Hexaamines: Electrocatalytic Hydrogen Evolution in Aqueous Solution.

The macrocyclic cobalt hexaamines [Co(trans-diammac)](3+) and [Co(cis-diammac)](3+) (diammac = 6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine) are capable of reducing the overpotential for hydrogen evolution on a mercury cathode in aqueous solution. Protons are reduced in a catalytic process involving reoxidation of the Co(II) species to its parent Co(III) complex. The cycle is robust at neutral pH with no decomposition of catalyst. The stability of the [Co(trans-diammac)](2+) and [Co(cis-diammac)](2+) complexes depends on the pH of the solution and the coordinating properties of the supporting electrolyte. Electrochemical studies indicate that the adsorbed Co(II) complex on the surface of mercury is the active catalyst for the reduction of protons to dihydrogen.

Journal Article↗
PubMed2000

Structural, spectroscopic, and electrochemical studies of binuclear manganese(II) complexes of bis(pentadentate) ligands derived from bis(1,4,7-triazacyclononane) macrocycles.

Structural, electrochemical, ESR, and H2O2 reactivity studies are reported for [Mn(dmptacn)Cl]ClO4 (1, dmptacn = 1,4-bis(2-pyridylmethyl)-1,4,7-triazacyclononane) and binuclear complexes of bis(pentadentate) ligands, generated by attaching 2-pyridylmethyl arms to each secondary nitrogen in bis(1,4,7-triazacyclononane) macrocycles and linked by ethyl (tmpdtne, [Mn2(tmpdtne)Cl2](ClO4)2.2DMF, 2), propyl (tmpdtnp, [Mn2(tmpdtnp)Cl2](ClO4)2.3H2O, 3), butyl (tmpdtnb, [Mn2(tmpdtnb)Cl2](ClO4)2.DMF.2H2O, 4), m-xylyl (tmpdtn-m-X, [Mn2(tmpdtn-m-X)-Cl2](ClO4)2, 5) and 2-propanol (tmpdtnp-OH, [Mn2(tmpdtnp-OH)Cl2](ClO4)2, 6) groups. 1 crystallizes in the orthorhombic space group P2(1)2(1)2(1) (No. 19) with a = 7.959(7) A, b = 12.30(1) A, and c = 21.72(2) A; 2, in the monoclinic space group P2(1)/c (No. 14) with a = 11.455(4) A, b = 15.037(6) A, c = 15.887(4) A, and beta = 96.48(2) degrees; 3, in the monoclinic space group P2(1)/c (No. 14) with a = 13.334(2) A, b = 19.926(2) A, c = 18.799(1) A, and beta = 104.328(8) degrees; and [Mn2(tmpdtnb)Cl2](ClO4)2.4DMF.3H2O (4'), in the monoclinic space group P2(1)/n (No. 14) with a = 13.361(3) A, b = 16.807(5) A, c = 14.339(4) A, and beta = 111.14(2) degrees. Significant distortion of the Mn(II) geometry is evident from the angle subtended by the five-membered chelate (ca. 75 degrees) and the angles spanned by trans donor atoms (< 160 degrees). The Mn geometry is intermediate between octahedral and trigonal prismatic, and for complexes 2-4, there is a systematic increase in M...M distance with the length of the alkyl chain. Cyclic and square-wave voltammetric studies indicate that 1 undergoes a 1e- oxidation from Mn(II) to Mn(III) followed by a further oxidation to MnIV at a significantly more positive potential. The binuclear Mn(II) complexes 2-5 are oxidized to the Mn(III) state in two unresolved 1e- processes [MnII2-->MnIIMnIII-->MnIII2] and then to the MnIV state [MnIII2-->MnIIIMnIV-->MnIV2]. For 2, the second oxidation process was partially resolved into two 1e- oxidation processes under the conditions of square-wave voltammetry. In the case of 6, initial oxidation to the MnIII2 state occurs in two overlapping 1e- processes as was found for 2-5, but this complex then undergoes two further clearly separated 1e- oxidation processes to the MnIIIMnIV state at +0.89 V and the MnIV2 state at +1.33 V (vs Fc/Fc+). This behavior is attributed to formation of an alkoxo-bridged complex. Complexes 1-6 were found to catalyze the disproportionation of H2O2. Addition of H2O2 to 2 generated an oxo-bridged mixed-valent MnIIIMnIV intermediate with a characteristic 16-line ESR signal.

Journal Article↗
PubMed2000

Macrocycle-supported titanium complexes with chelating imido ligands: analogues of ansa-metallocenes.

Reactions of 1,4-dimethyl-1,4,7-triazacyclononane (L1a) and 1,4-diisopropyl-1,4,7-triazacyclononane (L1b) to form 1-aminopropyl-4,7-di-R-1,4,7-triazacyclononane [R = Me (H2L3a) or Pri (H2L3b)] and 1-(2-aminobenzyl)-4,7-di-R-1,4,7-triazacyclononane [R = Me (H2L5a) or Pri (H2L5b)] are reported. Reaction of H2L3a and H2L5a with [Ti(NMe2)2Cl2] gives the ansa-linked macrocycle-imido complexes [Ti(kappa 4-L3a)Cl2] (5a) and [Ti(kappa 4-L5a)Cl2] (6a), respectively, and NHMe2. Reaction of H2L3a with [Ti(NBut)Cl2(py)3] gives [Ti(NBut)(kappa 3-H2L3a)Cl2] (7), which possesses a pendant alkylamine group that does not undergo amine/tert-butylimido group exchange to give 5a and ButNH2. However, reaction of H2L3b and H2L5b with [Ti(NBut)Cl2(py)3] does give amine/tert-butylimido group exchange to form [Ti(kappa 4-L3b)Cl2] (5b), [Ti(kappa 4-L5b)Cl2] (8b), and ButNH2. The compounds 5a,b and 6a,b are isolobal analogues of group 4 ansa-metallocene complexes and relatives of titanium cyclopentadienyl-amido constrained geometry olefin polymerization catalysts. Reaction of 5b with AgOTf affords [Ti(kappa 4-L3b)(OTf)Cl] (8) as the major product, the crystal structure of which has been determined. Alkylation of 6b by RLi gives the dialkyl derivatives [Ti(kappa 4-L5b)(R)2] [R = Me (9) or CH2SiMe3 (10)]. The ethylene polymerization capability of the compounds 5a,b, 6a,b, and 10 in the presence of methylaluminoxane has been determined and compared to that of [Ti(NBut)(kappa 3-L1a,b)Cl2] (11a,b); in all instances, low yields of high-molecular-weight polymer are obtained.

Journal Article↗
PubMed2000

Polyamine macrocycles incorporating a phenolic function: their synthesis, basicity, and coordination behavior toward metal cations. Crystal structure of a binuclear nickel complex.

The synthesis and characterization of two new polyazamacrocycles, 1,4,7,10-tetraaza[12](2,6)phenolphane (L1) and 1,4,7,10,13-pentaaza[15](2,6)phenolphane (L2), are reported. Both ligands incorporate the 2,6-phenolic unit within the cyclic framework. The basicity behavior and the ligational properties of L1 and L2 toward Ni(II), Zn(II), and Cu(II) were determined by means of potentiometric measurements in aqueous solution (298.1 +/- 0.1 K, I = 0.15 mol dm-3). UV spectra were used to understand the role of the phenolic function in the stabilization of the cations. L1 and L2 behave as pentaprotic bases under the experimental conditions used. The UV spectra showed that the deprotonation of the phenolic function occurs at low pH values for both ligands, giving rise to the simultaneous presence of positive and (one) negative charges on the macrocycle. While L1 forms only mononuclear complexes, L2 can also form binuclear species with all the metal ions investigated. In the mononuclear species of both ligands, one nitrogen atom close to the phenol remains unbound. The UV spectra revealed that the phenol, bridging the two metal ions in phenolate form, plays an important role in the stabilization of the binuclear complexes of L2. The coordination sphere of the two metals is completed by adding a secondary ligand such as water molecules or OH-, in any case preferring substrates able to bridge the two close metal ions. These results are confirmed by the crystal structure of [Ni2(C16H28ON5)(H2O)2Cl2]Cl.H2O.CH3OH (space group P21/a, a = 14.821(5) A, b = 10.270(4) A, c = 17.663(6) A, beta = 108.87(3) degrees, V = 2544(2) A3, Z = 4, R1 = 0.0973, wR2 = 0.2136). This structure displays a Ni(II) binuclear complex of L2 in which the phenolic oxygen and a chlorine ion bridge the two close Ni(II) ions.

Journal Article↗
PubMed2001

pH-dependent modulation of relaxivity and luminescence in macrocyclic gadolinium and europium complexes based on reversible intramolecular sulfonamide ligation.

A series of macrocyclic Eu, Gd, and Tb complexes has been prepared in which the intramolecular ligation of a beta-arylsulfonamide nitrogen is rendered pH-dependent, giving rise to changes in the hydration state, q, at the lanthanide center. In complexes based on DO3A, variation of the p-substituent in the arylsulfonamide moiety determines the apparent protonation constant log K(MLH) with values of 5.7, 6.4, and 6.7 for the -CF(3), -Me, and -OMe substituents, respectively. Introduction of three beta-carboxyalkyl substituents, alpha to three ring nitrogens, inhibits displacement of the bound water by added protein and also suppresses intermolecular binding by endogenous anions (lactate, HCO(3)(-)). Measurements of the pH dependence of the form and intensity of the Eu complexes revealed that intramolecular carboxylate coordination occurred competitively. This was reduced either by enhancing the electron density at the sulfonamide nitrogen or by enlarging the chelate ring from 7--8. Amplification of the relaxivity changes in the pH range 8--5 occurred on protein binding, and over the pH range 7.4--6.8 a 48% change in relaxivity was defined for [Gd.3a] (298 K, 65.6 MHz) in 50% human serum solution.

Journal Article↗
PubMed2002

Gold(I) macrocycles and topologically chiral [2]catenanes.

The design and synthesis of a new type of topologically chiral [2]catenane is reported. The compounds are formed easily by self-assembly on reaction of the oligomeric digold(I) diacetylide precursor complex [[4-BrC(6)H(4)CH(4-C(6)H(4)OCH(2)CCAu)(2)](n)] with diphosphine ligands. Reactions with the diphosphines PP = bis(diphenylphosphinophoshino)acetylene, trans-1,2-bis(diphenylphosphino)ethylene, bis(diphenylphosphino)ethane, and 1,1'-bis(diphenylphosphino)ferrocene yield simple ring complexes [4-BrC(6)H(4)CH(4-C(6)H(4)OCH(2)CCAu)(2)(mu-PP)] as the only products, since the spacer groups in the diphosphines are not long enough or are too bulky to allow catenane formation. Reaction with PP = bis(diphenylphosphino)propane or bis(diphenylphosphino)butane gave [2]catenane complexes [[4-BrC(6)H(4)CH(4-C(6)H(4)OCH(2)CCAu)(2)(mu-PP)](2)], whose structures are confirmed crystallographically. The macrocyclic ring compounds have C(s) symmetry but, as a result of the presence of the unsymmetrical "hinge group" 4-BrC(6)H(4)CH, the [2]catenanes have C(2) symmetry and so are topologically chiral. In favorable cases, the formation of the [2]catenane can be proved by NMR spectroscopy since catenane formation leads to nonequivalence of most ring atoms. The formation of the [2]catenanes was successfully predicted based on the conformation of the precursor bis(phenol), and it is argued that the methods used should be more generally applicable to the synthesis of functionally substituted supermolecules of interest for application in molecular devices.

Journal Article↗
PubMed2002

X-ray absorption and resonance Raman studies of methyl-coenzyme M reductase indicating that ligand exchange and macrocycle reduction accompany reductive activation.

Methyl-coenzyme M reductase (MCR) catalyzes methane formation from methyl-coenzyme M (methyl-SCoM) and N-7-mercaptoheptanoylthreonine phosphate (CoBSH). MCR contains a nickel hydrocorphin cofactor at its active site, called cofactor F(430). Here we present evidence that the macrocyclic ligand participates in the redox chemistry involved in catalysis. The active form of MCR, the red1 state, is generated by reducing another spectroscopically distinct form called ox1 with titanium(III) citrate. Previous electron paramagnetic resonance (EPR) and (14)N electron nuclear double resonance (ENDOR) studies indicate that both the ox1 and red1 states are best described as formally Ni(I) species on the basis of the character of the orbital containing the spin in the two EPR-active species. Herein, X-ray absorption spectroscopic (XAS) and resonance Raman (RR) studies are reported for the inactive (EPR-silent) forms and the red1 and ox1 states of MCR. RR spectra are also reported for isolated cofactor F(430) in the reduced, resting, and oxidized states; selected RR data are reported for the (15)N and (64)Ni isotopomers of the cofactor, both in the intact enzyme and in solution. Small Ni K-edge energy shifts indicate that minimal electron density changes occur at the Ni center during redox cycling of the enzyme. Titrations with Ti(III) indicate a 3-electron reduction of free cofactor F(430) to generate a stable Ni(I) state and a 2-electron reduction of Ni(I)-ox1 to Ni(I)-red1. Analyses of the XANES and EXAFS data reveal that both the ox1 and red1 forms are best described as hexacoordinate and that the main difference between ox1 and red1 is the absence of an axial thiolate ligand in the red1 state. The RR data indicate that cofactor F(430) undergoes a significant conformational change when it binds to MCR. Furthermore, the vibrational characteristics of the ox1 state and red1 states are significantly different, especially in hydrocorphin ring modes with appreciable C=N stretching character. It is proposed that these differences arise from a 2-electron reduction of the hydrocorphin ring upon conversion to the red1 form. Presumably, the ring-reduction and ligand-exchange reactions reported herein underlie the enhanced activity of MCR(red1), the only form of MCR that can react productively with the methyl group of methyl-SCoM.

Electron Spin Resonance Spectroscopy↗
PubMed2002

Macrocyclic aromatic ether-imide-sulfones: versatile supramolecular receptors with extreme thermochemical and oxidative stability.

Macrocyclic receptors having extreme thermo-oxidative stability, and which bind a wide range of electron-donor substrates via pi-stacking donor-acceptor interactions, are accessible by cycloimidization of an amine-functionalized aryl ether-sulfone with pyromellitic dianhydride or 1,4,5,8-naphthalenetetracarboxylic dianhydride. The potential of these receptors in supramolecular chemistry is illustrated, for example, by the spontaneous self-assembly and crystallization of a five-component [3]pseudorotaxane from a solution of its constituents.

Journal Article↗