Supramolecular Assembly of Ag(I) Centers: Diverse Topologies Directed by Anionic Interactions.

Ag(I)-Ag(I) interactions in supramolecular structures have been achieved through the use of structural support from the ligand frames. In structures involving simple ligands like pyridine, strong π-π interaction leads to spatial ordering of the individual [Ag(L)2]+ units. In such structures anions also play a crucial role in dictating the final arrangement of the [Ag(L)2]+ synthons. In order to determine whether the anions can solely dictate the arrangement of the [Ag(L)2]+ synthons in the supramolecular structure, four Ag(I) complexes of 4-pyridylcarbinol (PyOH), namely, [Ag(PyOH)2]X (X = NO3- (1), BF4- (2), CF3SO3- (3), and ClO4- (4)) have been synthesized and structurally characterized. Gradual transformation of the extended structures observed in 1-3 eventually merges into a unique linear alignment of the [Ag(PyOH)2]+ units in 4 along the c axis, a feature that results in strong argentophilic interactions. Complex 4 is sensitive to light and is inherently less stable than the other three analogues. The structural variations in this set of extended assemblies are solely dictated by the anions, since π-π interaction between the substituted pyridine ligands is significantly diminished due to disposition of the -CH2OH substituent at the 4 position and H-bonding throughout the structure.

Endohedral fullerene with µ3-carbido ligand and titanium-carbon double bond stabilized inside a carbon cage.

In all metallofullerenes known before this work, metal atoms form single highly polar bonds with non-metal atoms in endohedral cluster. This is rather surprising for titanium taking into account the diversity of organotitanium compounds. Here we show that the arc-discharge synthesis of mixed titanium-lutetium metallofullerenes in the presence of ammonia, melamine or methane unexpectedly results in the formation of TiLu2C@I(h)-C80 with an icosahedral Ih(7) carbon cage. Single-crystal X-ray diffraction and spectroscopic studies of the compound reveal an unprecedented endohedral cluster with a µ3-carbido ligand and Ti-C double bond. The Ti(IV) in TiLu2C@I(h)-C80 can be reversibly reduced to the Ti(III) state. The Ti = C bonding and Ti-localized lowest unoccupied molecular orbital in TiLu2C@Ih-C80 bear a certain resemblance to titanium alkylidenes. TiLu2C@I(h)-C80 is the first metallofullerene with a multiple bond between a metal and the central, non-metal atom of the endohedral cluster.

Bioorganometallic chemistry. 13. Regioselective reduction of NAD(+) models, 1-benzylnicotinamde triflate and beta-nicotinamide ribose-5'-methyl phosphate, with in situ generated [CpRh(Bpy)H](+): structure-activity relationships, kinetics, and mechanistic aspects in the formation of the 1,4-NADH derivatives.

Cofactor regeneration; i.e., regiospecific conversion of NAD(+) to 1,4-NADH, has been extensively studied and is a crucial component in the eventual use of 1,4-NADH in a variety of bioorganic synthesis processes involving the formation of chiral organic compounds. We have studied the reduction of a model NAD(+) compound, 1-benzylnicotinamide triflate, 1a, using [CpRh(bpy)(H(2)O)](2+), 2 (Cp = eta(5)-C(5)Me(5), bpy = 2,2'-bipyridyl), as the catalyst precursor and sodium formate (HCO(2)Na) as the hydride source in 1:1 H(2)O/THF and have found exclusive 1-benzyl-1,4-dihydronicotinamide regioselectivity, as was observed previously for natural NAD(+) that provided 1,4-NADH (see: Steckhan et al. Organometallics 1991, 10, 1568). Moreover, a variety of 3-substituted derivatives of 1-benzylpyridinium triflate, in addition to the -C(O)NH(2) group (1a), were also studied to ascertain that this 3-functionality (e.g., -C(O)NHCH(3), -C(S)NH(2), -C(O)CH(3), -C(O)OCH(3), and -CN, 1b,d-g) coordinates to a [CpRh(bpy)H](+) complex to direct the concerted, regioselective transfer of the hydride group from the rhodium to the 4-ring position of the NAD(+) model; all coordinating 3-substituents had relative rates in the 0.9-1.3 range with substrate 1a set to 1.0. If in fact the 3-substituent presented a steric effect [-C(O)NH(CH(2)CH(3))(2), 1c] or was a nonbinding group (-CH(3), 1h; -H, 1i), no catalytic hydride transfer was observed even with the more electrophilic 2 and 6 ring positions being readily available, which further implicated the crucial coordination of the NAD(+) model to the CpRh metal ion center. We also found that the 1-benzyl substituent on the nitrogen atom exerted a substantial electron-withdrawing effect, in comparison to the electron-donating 1-methyl substituent, and favorably affected the rate of the regioselective reduction (rate enhancement of 1-benzyl/1-methyl = 2.0). The kinetics of the regioselective reduction of 1a were studied to show that the initial rate of reduction, r(i), is affected by the concentrations of the substrate, 1a, precatalyst, 2, and the hydride source, HCO(2)Na, in 1:1 H(2)O/THF: d[1-benzyl-1,4-dihydronicotnamide]/dt = k(cat)[1a][2][HCO(2)Na]. Furthermore, we wish to demonstrate that a previously synthesized aqueous NAD(+) model, beta-nicotinamide ribose-5'-methyl phosphate, 3, shows a similar regioselectivity for the 1,4-NADH analogue, while the initial rate (r(i)) for the regioselective reduction of 3 and NAD(+) itself was found to be comparable in water but faster by a factor of approximately 3 in comparison to 1a in 1:1 H(2)O/THF; the solvent, THF, appeared to inhibit the rate of reduction in 1a by presumably competing with the substrate 1a for the CpRh metal ion center. However, in H(2)O, the initial kinetic rate for substrate 3 was not affected by its concentration and implies that, in H(2)O, [CpRh(bpy)H](+) formation is rate determining. We assume that binding of 3 and NAD(+) to the CpRh metal ion center is also a pertinent step for 1,4-dihydro product formation, the experimental rate expression in H(2)O being d[1,4-dihydro-beta-nicotinamide ribose-5'-methyl phosphate]/dt = k(cat)[2][HCO(2)Na]. What we have discovered, for the first time, is evidence that the regioselective reduction of NAD(+) to 1,4-NADH by [CpRh(bpy)H](+) is a consequence of the amide's ability to coordinate to the CpRh metal center, thereby constricting the kinetically favorable six-membered ring transition state for plausible concerted hydride transfer/insertion to C4 to regioselectively provide the 1,4-NADH derivative; [CpRh(bpy)H](+) can be categorized as a biomimetic enzymatic hydride via its ability to bind and regioselectively transfer hydride to C4, exclusively. Clearly, the pyrophosphate and adenosine groups associated with the structure of NAD(+) are not essential in the rate of hydride transfer to C4, with NAD(+) model 3 having a similar initial rate (r(i)) of reduction as NAD(+) itself in water. Finally, a catalytic cycle will be proposed to account for our overall observations.

Conversion of azomethine moiety to carboxamido group at cobalt(III) center in model complexes of Co-containing nitrile hydratase.

The Co(III) complex of the Schiff base ligand N-2-mercaptophenyl-2'-pyridylmethyl-enimine (PyASH), namely, [Co(PyAS)(2)]Cl (1), has been synthesized via an improved method and its structure has been determined by X-ray crystallography. The two deprotonated ligands are arranged in mer configuration around the Co(III) center and the overall coordination geometry is octahedral. The coordinated azomethine function in 1 is rapidly converted into carboxamido group upon reaction with OH(-). The product is the bis carboxamido complex (Et(4)N)[Co(PyPepS)(2)] (2), reported by us previously. Reaction of H(2)O(2) with 1 in DMF affords [Co(PyASO(2))(PyPepSO(2))] (3), a species with mixed imine and carboxamido-N donor centers as well as S-bound sulfinates. Further reaction with H(2)O(2) in the presence of NaClO(4) converts 3 into the previously reported bis carboxamido/sulfinato complex Na[Co(PyPepSO(2))(2)] (4). The reaction conditions for the various transformation reactions for complexes 1-4 and the structure of 3 are also reported. The mechanism of the -CH=NR + [O] --> -C(=O)NHR transformation has been discussed. The reactions reported here provide convenient alternate routes for the syntheses of Co(III) complexes with coordinated carboxamide, thiolate, and/or sulfinate donors as models for the Co-site in the Co-containing nitrile hydratase(s).

A remarkable skeletal rearrangement of a coordinated tetrapyrrole: chemical consequences of palladium pi-coordination to a bilindione.

Pd4(OEB)2, in which a [Pd2]2+ unit is bound in pi-fashion to olefinic sites that are exocyclic to pyrrole rings of the octaethylbilindione ligand, undergoes an unprecedented sequence of reactions that results in the rearrangement of the framework of the bilindione ligand and the formation of trans-Pd(py)2I2. This process of bilindione rearrangement and oxidation occurs as a direct consequence of the pi-coordination of the palladium. The reaction results in the migration of a nitrogen atom from a pyrrole carbon atom to what was formerly a meso carbon atom to transform a former pyrrole ring into a six-membered ring. This process also involves cleavage of the Pd-Pd and Pd-C bonds, oxidation of palladium, and introduction of an oxygen atom (from water) not necessarily in this particular sequence.

Ring-opening and meso substitution from the reaction of cyanide ion with zinc verdohemes.

The reactivity of zinc verdoheme, [Zn(II)(OEOP)](O(2)CCH(3)) where OEOP is the monoanion of octaethyl-5-oxaporphyrin, with cyanide ion has been shown to be a complex process that involves not only the expected ring-opening of the macrocycle, as occurs with other nucleophiles (methoxide, methanethiolate, dimethylamide), but also substitution at one or two of the meso positions. The ring-opened products have been subjected to crystallographic study. The structures of mu-H(2)O-[Zn(II)(OEB-10,19-(CN)(2))](2) and mu-H(2)O-[(Zn(II)(OEB-10,15,19-(CN)(3))](2) both consist of two helical tetrapyrrole subunits that are coordinated to a zinc ion through four Zn-N bonds. The two zinc ions are coordinated to a bridging water molecule that is also hydrogen bonded to a lactam oxygen atom at one end of each tetrapyrrole subunit. Thus the chiral sense of one helical Zn(II)(OEB-10,19-(CN)(2)) portion is transmitted to the other Zn(II)(OEB-10,19-(CN)(2)) unit and the resulting binuclear unit is chiral. In contrast Co(II)(OEB-15,19-(CN)(2)), which was obtained by the insertion of Co(II) into the free ligand, is monomeric with a four-coordinate cobalt ion. A series of DFT geometry optimization calculations were performed on zinc complexes of 5-oxaporphyrins (verdoheme), verdins (bilindione), 4-cyano-5-oxaporphyrins, and 19-cyanoverdins in an effort to gain insights to the features of these complexes and the reactions that lead to meso-cyano-substituted cyanoverdins.

Vinyl sulfones in solid-phase synthesis: preparation of 4,5,6,7-tetrahydroisoindole derivatives.

The preparation of functionalized 4,5,6,7-tetrahydroisoindole via a traceless solid-phase sulfone linker strategy is described. Thermolytic extrusion of SO(2) from polymer-bound 3-(phenylsulfonyl)-3-sulfolene (7) generated polymer-bound 2-(phenylsulfonyl)-1,3-butadiene (9) in situ which underwent Diels--Alder cycloaddition with various dienophiles to furnish vinyl sulfone resins 10-14. To complete a traceless linker cleavage strategy, (p-tolysulfonyl)methyl isocyanide or ethyl isocyanoacetate was employed to react with the vinyl sulfone moiety to liberate functionalized 4,5,6,7-tetrahydroisoindole products from the resin. Using this chemistry, nine tetrahydroisoindole derivatives (6, 15-22) were prepared in 32-41% overall yields from polystyrene/divinylbenzene sulfinate 1.

Alteration of the aurophilic interactions in trimeric gold(I) compounds through charge transfer. Behavior of solvoluminescent Au(3)(MeN=COMe)(3) in the presence of electron acceptors.

The ability of the triangular gold(I) complex, Au(3)(MeN=COMe)(3), which as a solid displays the novel property of solvoluminescence (see: Vickery, J. C.; Olmstead, M. M.; Fung, E. Y.; Balch, A. L. Angew.Chem., Int. Ed. Engl. 1997, 36, 1179) to function as an electron donor has been demonstrated through spectroscopic studies and isolation of crystalline adducts with organic acceptor molecules. Four such adducts with nitro-9-fluorenones have been isolated and subject to single-crystal X-ray diffraction study. These are deep yellow [Au(3)(MeN=COMe)(3)].[2,4,7-trinitro-9-fluorenone], red [Au(3)(MeN=COMe)(3)].[2,4,5,7-tetranitro-9-fluorenone], red [Au(3)(MeN=COEt)(3)](2).[2,7-dinitro-9-fluorenone], and red [Au(3)(MeN=COEt)(3)](2).[2,4,7-trinitro-9-fluorenone]. The solid-state structures of [Au(3)(MeN=COMe)(3)].[2,4,7-trinitro-9-fluorenone] and [Au(3)(MeN=COMe)(3)].[2,4,5,7-tetranitro-9-fluorenone] consist of columns in which the planar gold(I) trimers and the nearly planar nitro-9-fluorenones are interleaved with the gold trimers making face-to-face contact with the nitroaromatic portion of the electron acceptor. Thus the organic acceptors disrupt the aurophilic interactions present in crystalline [Au(3)(MeN=COMe)(3)] itself. However, in [Au(3)(MeN=COEt)(3)](2).[2,7-dinitro-9-fluorenone] and [Au(3)(MeN=COEt)(3)](2).[2,4,7-trinitro-9-fluorenone], aurophilic interactions are found which produce dimers, [Au(3)(MeN=COEt)(3)](2), with nearly trigonal prismatic Au(6) cores. These dimers are interleaved with the nitro-9-fluorenone molecules to again form extended columns in which the components make face-to-face contact. Despite the fact that the gold atoms in [Au(3)(MeN=COMe)(3)] and [Au(3)(MeN=COEt)(3)] are in exposed sites and only two-coordinate, there is no evidence of additional coordination of the nitro-9-fluorenones with gold centers in the crystalline adducts.

A synthetic analogue of the active site of Fe-containing nitrile hydratase with carboxamido N and thiolato S as donors: synthesis, structure, and reactivities.

As part of our work on models of the iron(III) site of Fe-containing nitrile hydratase, a designed ligand PyPSH(4) with two carboxamide and two thiolate donor groups has been synthesized. Reaction of (Et(4)N)[FeCl(4)] with the deprotonated form of the ligand in DMF affords the mononuclear iron(III) complex (Et(4)N)[Fe(III)(PyPS)] (1) in high yield. The iron(III) center is in a trigonal bipyramidal geometry with two deprotonated carboxamido nitrogens, one pyridine nitrogen, and two thiolato sulfurs as donors. Complex 1 is stable in water and binds a variety of Lewis bases at the sixth site at low temperature to afford green solutions with a band around 700 nm. The iron(III) centers in these six-coordinate species are low-spin and exhibit EPR spectra much like the enzyme. The pK(a) of the water molecule in [Fe(III)(PyPS)(H(2)O)](-) is 6.3 +/- 0.4. The iron(III) site in 1 with ligated carboxamido nitrogens and thiolato sulfurs does not show any affinity toward nitriles. It thus appears that at physiological pH, a metal-bound hydroxide promotes hydration of nitriles nested in close proximity of the iron center in the enzyme. Redox measurements demonstrate that the carboxamido nitrogens prefer Fe(III) to Fe(II) centers. This fact explains the absence of any redox behavior at the iron site in nitrile hydratase. Upon exposure to limited amount of dioxygen, 1 is converted to the bis-sulfinic species. The structure of the more stable O-bonded sulfinato complex (Et(4)N)[Fe(III)(PyP[SO(2)](2))] (2) has been determined. Six-coordinated low-spin cyanide adducts of the S-bonded and the O-bonded sulfinato complexes, namely, Na(2)[Fe(III)(PyP[SO(2)](2))(CN)] (4) and (Et(4)N)(2)[Fe(III)(PyP[SO(2)](2))(CN)] (5), afford green solutions in water and other solvents. The iron(II) complex (Et(4)N)(2)[Fe(II)(PyPS)] (3) has also been isolated and structurally characterized.

Synthesis and reactions of some heterocyclic azacyanines.

The one-step reaction of some amino-substituted heterocycles with diiodomethane to give azacyanines is reported. This useful reaction is of wider application than initially reported and includes the synthesis of new substituted pyrido-, isoquino-, benzimadazo-, and benzothiazoazacyanines 7. Furthermore, treatment of these azacyanines with base generally affects a facile opening of the dihydrotriazinium ring resulting in the formation of new heterocycles 10, 11, and 12, which would be difficult to prepare by other means. This reaction takes an additional direction in the case of halo-substituted azacyanines 7b/c/d where treatment with base gives rise to new interesting derivatives of dipyridotriazines 14b/c/d.

A mixed oxidation state, binuclear iron complex containing an unsymmetrically coordinating ligand. A ligand-induced switch in redox behavior.

Binuclear [FeIIFeIII(BMDP)(O2CPh)3](BF4) (1) was obtained by treating an acetonitrile solution of the fully reduced [FeIIFeII(BMDP)(O2CPh)(MeOH)1.5(H2O)0.5](BF4)2 with 5 equiv of benzoate and then exposing the mixture to oxygen. Examination of [FeIIFeIII(BMDP)(O2CPh)3](BF4) by X-ray crystallography reveals the localized, mixed oxidation state nature of the cation in the solid state. 1H NMR and magnetic susceptibility data for the new complex are also reported. In the absence of dioxygen and other oxidants, treatment of FeIIFeII(BMDP)(O2CPh)(MeOH)1.5(H2O)0.5](BF4)2 with excess benzoate results in the formation of [FeIIFeII(BMDP)(O2CPh)2](BF4)2, which has also been characterized by X-ray diffraction.

Addition of diprotic nucleophiles to a C60-tetrazine monoadduct: structural reassignment and correction of a novel rearrangement.

C60-tetrazine Diels-Alder adducts bearing electron deficient dihydropyridazine groups undergo chemoselective amination and hydration reactions upon addition of primary aliphatic amines and water, respectively, to form new adducts with 4,5-dihydropyrazole groups nested atop the [60]fullerene skeleton.

Structure-spectroscopy correlation in distorted five-coordinate Cu(II) complexes: a case study with a set of closely related copper complexes of pyridine-2,6-dicarboxamide ligands.

Eight Cu(II) complexes with the [Cu(dmppy)] moiety (dmppyH(2) = tridentate ligand N,N'-dimethylpyridine-2,6-dicarboxamide; H's are dissociable amide protons) and ligands like pyridine, water, N-methylimidazole, substituted and unsubstituted o-phenanthroline, and bipyridine have been isolated and structurally characterized. The basal angles of these structurally related five-coordinate Cu(II) complexes (and two previously reported ones) correlate well with the EPR hyperfine splitting parameter A( parallel). However, the values of the parameter tau which provides a measure of the degree of square pyramid versus trigonal bipyramid geometry adopted by these complexes do not correlate linearly with the A( parallel) values. It is evident that out-of-plane distortions and ligand strain make calculation of tau inconsistent in certain sets of five-coordinate Cu(II) complexes. Structure-spectroscopy correlation involving tau is not feasible in such cases.

Monomeric and dimeric copper(II) complexes of a novel tripodal peptide ligand: structures stabilized via hydrogen bonding or ligand sharing.

The novel tripodal ligand N-(bis(2-pyridyl)methyl)-2-pyridinecarboxamide (Py3AH) affords monomeric and dimeric copper(II) complexes with coordinated carboxamido nitrogens. Although many chloro-bridged dimeric copper(II) complexes are known, [Cu(Py3A)(Cl)] (1) remains monomeric and planar with a pendant pyridine and does not form either a chloro-bridged dimer or the ligand-shared dimeric complex [Cu(Py3A)(Cl)]2 (4) in solvents such as CH3CN. When 1 is dissolved in alcohols, square pyramidal alcohol adducts [Cu(Py3A)(Cl)(CH3OH)] (2) and [Cu(Py3A)(Cl)(C2H5OH)] (3) are readily formed. In 2 and 3, the ROH molecules are bound at axial site of copper(II) and the weak axial binding of the ROH molecule is strengthened by intramolecular hydrogen bonding between ROH and the pendant pyridine nitrogen. Two ligand-shared dimeric species [Cu(Py3A)(Cl)]2 (4) and [Cu(Py3A)]2(ClO4)2 (5) have also been synthesized in which the pendant pyridine of one [Cu(Py3A)] unit completes the coordination sphere of the other [Cu(Py3A)] neighbor. These ligand-shared dimers are obtained in aqueous solutions or in complete absence of chloride in the reaction mixtures.

Co(III) complexes with coordinated carboxamido nitrogens and thiolato sulfurs as models for Co-containing nitrile hydratase and their conversion to the corresponding sulfinato species.

Recent spectroscopic data suggest that the Co(III) site in Co-containing nitrile hydratase is ligated to carboxamido nitrogens and thiolato sulfurs and most possibly one or more of the bound thiolates exist as sulfenato and/or sulfinato groups. The absence of any Co(III) complex with such coordination makes it quite difficult to predict the reactivity of this kind of Co(III) site. In this paper, the Co(III) complexes of two designed ligands PyPepSH2 (1) and PyPepRSH2 (2) have been reported. The two complexes, namely, (Et4N)[Co(PyPepS)2] (3) and Na[Co(PyPepRS)2] (4) are the first examples of Co(III) complexes with carboxamido nitrogens and thiolato sulfurs as donors. The average Co(III)-Namido and Co(III)-S distances in these complexes lie in the range 1.90-1.92 and 2.22-2.24 A, respectively. Reaction of H2O2 with both complexes readily affords Na[Co(PyPepSO2)2] (5) and Na[Co(PyPepRSO2)2] (6), species in which the thiolato sulfurs are converted to sulfinato (SO2) groups. Such conversion also occurs when solutions of 3 and 4 are exposed to dioxygen in the presence of activated charcoal. These reactions are clean and the S --> SO2 transformation does not introduce significant changes in the metric parameters of these complexes. The reactivity of 3 and 4 indicates that the bound Cys-sulfurs around the biological Co(III) site could be oxidized to sulfinato groups.

Redox characteristics of nickel and palladium complexes of the open-chain tetrapyrrole octaethylbilindione: a biliverdin model.

Octaethylbiliverdin, C35H46N4O2, is a linear tetrapyrrole that can exist in coordinated form as the fully reduced trianion (OEB)3-, as the two electron oxidized monoanion, (OEBOx)-, or as the one electron oxidized radical, (OEB.)2-. The three-membered electron-transfer series involving [M(OEB)]n with n = +1, 0, and -1, and M = Ni or Pd has been characterized electrochemically. The most highly oxidized members of these series have been isolated in the form of their diamagnetic triiodide salts, [NiII(OEBOx)]I3 and [PdII(OEBOx)]I3, and characterized spectroscopically and by X-ray diffraction. [NiII(OEBOx)]I3 crystallizes in the orthorhombic space group Pbcn with a = 15.121(3) A, b = 16.777(3) A, and c = 14.628(3) A at 130(2) K with Z = 4. Refinement of 3311 reflections with 209 parameters and no restraints yielded wR2 = 0.136 and R = 0.054 for 2643 reflections with I > 2 sigma(I). The structure involves helical coordination of the linear tetrapyrrole ligand about the nickel with all four nitrogen atoms coordinated to the metal and Ni-N distances of 1.867(5) and 1.879(5) A. The triiodide ion is not coordinated to the nickel but sits over one of the meso carbon atoms of the tetrapyrrole. In the solid state, pairs of [NiII(OEBOx)]+ crystallize about a center of symmetry so that two identical tab/slot hydrogen-bonded arrangements involving the lactam oxygen of one complex and methine and two methylene protons of the adjacent cation. Similar hydrogen-bonded motifs are found in other complexes derived from octaethylbilindione. [PdII(OEBOx)]I3 is isomorphic with the nickel analogue and crystallizes in the orthorhombic space group Pbcn with a = 15.2236(6) A, b = 16.7638(7) A, and c = 14.6289(6) A at 90(2) K with Z = 4. Refinement of 6123 reflections with 209 parameters and no restraints yielded wR2 = 0.094 and R = 0.036 for 4042 reflections with I > 2 sigma(I). The odd electron compound PdII(OEB.) has also been isolated and characterized by single-crystal X-ray diffraction. Black PdII(OEB.) crystallizes in the monoclinic space group I2/a with a = 13.274(3) A, b = 18.655(4) A, c = 14.114(3) A, and beta = 116.00(3) degrees at 140(2) K with Z = 4. Refinement of 2030 reflections with 195 parameters and no restraints yielded wR2 = 0.090 and R = 0.042 for 1715 reflections with I > 2 sigma(I). The structure again involves helical coordination of the linear tetrapyrrole to the palladium through the four pyrrole nitrogen atoms. Reduction of the complex causes a slight elongation of the Pd-N bonds from 1.983(2) and 1.986(2) A in [PdII(OEBOx)]I3 to 2.011(4) and 2.012(4) A in PdII(OEB.).

Synthesis, characterization, and polymerization activity of [bis(4,4'-bis(neophyldimethylsilylmethyl)-2,2'-bipyridyl)copper(I)]+CuBr2- and Implications for copper(I) catalyst structures in atom transfer radical polymerization.

A series of 4,4'-disilyl-substituted-2,2'-bipyridine ligands were prepared using a metathesis reaction of the dianion of 4,4'-dimethyl-2,2'-bipyridine with several trialkylsilyl chlorides: 4,4'bis(tert-butyldimethylsilylmethyl)-2,2'-bipyridine (dTBDMSbipy), 4,4'-bis(dimethylthexylsilylmethyl)-2,2'-bipyridine (dTHEXbipy), and 4,4'-bis(neophyldimethylsilylmethyl)-2-2'-bipyridine (dNEObipy). It was observed that the side chain length correlated with the ability of the ligand to form hydrocarbon soluble complexes of copper(I) bromide, with dNEObipy forming the most soluble and easily crystallized complexes. The atom transfer radical polymerization (ATRP) of styrene using dNEObipy as the ligand displayed molecular weight control equivalent to other ATRP systems in which solubilizing ligands, such as 4,4'-di-5-nonyl-2,2'-bipyridine or 4,4'-di-n-heptyl-2,2'-bipyridine, were used. The one-to-one complex of dNEObipy with CuBr was prepared and its crystal structure was determined. The resulting complex had the ionic formulation [(dNEObipy)2Cu]+[CuBr2]- and displayed similar activities in styrene ATRP as the standard 2 dNEObipy/CuBr catalyst system. These and other polymerization results in addition to NMR experiments suggest that the predominant copper(I) species formed in ATRP solutions is the 2-to-1 ligand-to-copper(I) cation, [(dNEObipy)2Cu]+, with either a dihalocuprate or halide counteranion, depending upon the conditions.

Nickel complexes of 21-oxaporphyrin and 21, 23-dioxaporphyrin.

The nickel(I) and nickel(II) complexes of 5,20-bis(p-tolyl)-10, 15-diphenyl-21-oxaporphyrin (ODTDPPH) and 5,10,15,20-tetraphenyl-21, 23-dioxaporphyrin (O2 TPP) have been investigated. These oxa analogues of 5,10,15,20-tetraarylporphyrin, where one or two pyrrole rings are replaced by a furan moiety, have been synthesized by condensation of the respective precursors, namely 2,5-bis(arylhydroxymethyl)furan, pyrrole, and arylaldehyde. Insertion of nickel(II) into ODTDPPH or O2 TPP yielded high-spin five- and six-coordinate ([(ODTDPP)Ni(II) Cl] and [(O2 TPP)NiIICl2 ]) complexes, which can be reduced with moderate reducing reagents. The EPR spectra of [(ODTDPP)Ni(I) ] and [(O2 TPP)Ni(I) Cl] revealed the Ni(I) oxa(dioxa)porphyrin rather than a Ni(I) anion radical electronic structure. In the structures of [(ODTDPP)Ni(II) Cl], [(O2 TPP)Ni(IICl) 2 ], and [(ODTDPP)Ni(I) ], determined by X-ray diffraction, the furan ring is planar and coordinates in the η(1) fashion through the trigonal oxygen atom; the nickel ion lies in the furan plane for the latter two complexes, but slightly outside it in [(ODTDPP)Ni(II) Cl]. The Ni-N and Ni-O bond lengths decrease upon reduction of high-spin five-coordinate [(ODTDPP)Ni(II) Cl] to four-coordinate [(ODTDPP)Ni(I) ]. The pattern of downfield pyrrole resonances in (1) H NMR spectra of [(ODTDPP)Ni(IICl) ] and [(O2 TPP)-Ni(II) Cl2 ] has been established. The downfield positions of furan resonances are unusual for Ni(II) heteroporphyrins; they have been accounted for by the nearly in-plane coordination of the furan moiety as opposed to the side-on coordination found for thiophene- or selenophene-containing heteroporphyrins. An example of ion-pair formation, [(O2 TPPH)2 ][Ni(II) Cl4 ], was produced from [(O2 TPP)Ni(II) Cl2 ] by acidification with HCl.