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The syntheses and X-ray structures of two molybdenum pyranopterin dithiolene complexes in biologically relevant Mo(4+) and Mo(5+) states are reported. Crystallography reveals that these complexes possess a pyran ring formed through a spontaneous cyclization reaction of a dithiolene side-chain hydroxyl group at a C═N bond of the pterin. NMR data on the Mo(4+) complex suggest that a reversible pyran ring cyclization occurs in solution. These results provide experimental evidence that the pyranopterin dithiolene ligand in molybdenum and tungsten enzymes could participate in catalysis through dynamic processes modulated by the protein.

The synthesis, characterization, binding to calf thymus DNA, and plasmid DNA photocleavage studies of two ruthenium(II) pteridinylphenanthroline complexes are reported where the new pteridinylphenantholine ligands in these complexes are additions to a larger family designed to resemble DNA bases. [Ru(bpy)(2)(L-keto)](PF(6))(2)1 is synthesized from ligand substitution of Ru(bpy)(2)Cl(2) by 4-keto-pteridino[6,7-f]phenanthroline (L-keto). Increasing the reaction temperature during synthesis of 1 causes a ring scission of the L-keto ligand within the pyrimidine ring yielding a second Ru complex, [Ru(bpy)(2)(L-aap)](PF(6))(2)2 where L-aap is 2-amino-3-amidopyrazino[5,6-f]phenanthroline. The ring cleavage reaction is accompanied by the loss of one carbon in the pyrimidine ring. Complexes 1 and 2 are characterized by (1)H NMR, UV/visible absorption and FT-IR spectroscopies and by cyclic voltammetry, and these results are presented in comparison to the previously reported related complexes [Ru(bpy)(2)(L-allox)](PF(6))(2), [Ru(bpy)(2)(L-amino)](PF(6))(2), and [Ru(bpy)(2)(dppz)](PF(6))(2). In addition, 2 has been structurally characterized by X-ray diffraction. Both 1 and 2 are good intercalators of calf thymus DNA as determined by viscometry and binding constants obtained from absorption titrations. Only the ring-cleaved complex 2 exhibits a high degree of pBR322 plasmid photocleavage in contrast to the other pteridinyl-phenanthroline complexes, which exhibit no plasmid DNA photocleavage. Complex 1, however, decomposes in buffer forming the photocleaver 2, demonstrating that sample age and reactivity can affect observed photocleavage. Complex 2 appears to photocleave DNA through a singlet oxygen mechanism.

The molybdenum cofactor at the catalytic heart of mononuclear molybdoenzymes comprises a molybdenum ion coordinated by one or two dithiolene ligands containing an N-heterocyclic structure known as pterin. Understanding the details of the unusual combination of molybdenum with pterin and dithiolene is the impetus behind employing model chemistry to investigate the cofactor’s broad redox capabilities. This chapter highlights the major efforts to synthesize pterin-containing models and study their chemical properties. The history of identification of the cofactor’s pyranopterin dithiolene ligand and the details of pterin redox chemistry are reviewed, followed by an account of the synthesis and analysis of pterin-inspired chemical models. The implications of these models’ chemical reactivity and redox features that provide a fundamental basis for understanding the molybdenum cofactor are included. In addition, we highlight the potential directions of the field.

The molybdenum cofactor is composed of a molybdenum coordinated by one or two rather complicated ligands known as either molybdopterin or pyranopterin. Pterin is one of a large family of bicyclic N-heterocycles called pteridines. Such molecules are widely found in Nature, having various forms to perform a variety of biological functions. This article describes the basic nomenclature of pterin, their biological roles, structure, chemical synthesis and redox reactivity. In addition, the biosynthesis of pterins and current models of the molybdenum cofactor are discussed.

The interactions of five bis(bipyridyl) Ru(II) complexes of pteridinyl-phenanthroline ligands with calf thymus DNA have been studied. The pteridinyl extensions were selected to provide hydrogen-bonding patterns complementary to the purine and pyrimidine bases of DNA and RNA. The study includes three new complexes [Ru(bpy)(2)(L-pterin)](2+), [Ru(bpy)(2)(L-amino)](2+), and [Ru(bpy)(2)(L-diamino)](2+) (bpy is 2,2'-bipyridine and L-pterin, L-amino, and L-diamino are phenanthroline fused to pterin, 4-aminopteridine, and 2,4-diaminopteridine), two previously reported complexes [Ru(bpy)(2)(L-allox)](2+) and [Ru(bpy)(2)(L-Me(2)allox)](2+) (L-allox and L-Me(2)allox are phenanthroline fused to alloxazine and 1,3-dimethyalloxazine), the well-known DNA intercalator [Ru(bpy)(2)(dppz)](2+) (dppz is dipyridophenazine), and the negative control [Ru(bpy)(3)](2+). Reported are the syntheses of the three new Ru-pteridinyl complexes and the results of calf thymus DNA binding experiments as probed by absorption and fluorescence spectroscopy, viscometry, and thermal denaturation titrations. All Ru-pteridine complexes bind to DNA via an intercalative mode of comparable strength. Two of these four complexes--[Ru(bpy)(2)(L-pterin)](2+) and [Ru(bpy)(2)(L-allox)](2+)--exhibit biphasic DNA melting curves interpreted as reflecting exceptionally stable surface binding. Three new complexes--[Ru(bpy)(2)(L-diamino)](2+), [Ru(bpy)(2)(L-amino)](2) and [Ru(bpy)(2)(L-pterin)](2+)--behave as DNA molecular "light switches."

The conserved pterin dithiolene ligand that coordinates molybdenum (Mo) in the cofactor (Moco) of mononuclear Mo enzymes can exist in both a tricyclic pyranopterin dithiolene form and as a bicyclic pterin-dithiolene form as observed in protein crystal structures of several bacterial molybdoenzymes. Interconversion between the tricyclic and bicyclic forms via pyran scission and cyclization has been hypothesized to play a role in the catalytic mechanism of Moco. Therefore, understanding the interconversion between the tricyclic and bicyclic forms, a type of ring-chain tautomerism, is an important aspect of study to understand its role in catalysis. In this study, equilibrium constants (K(eq)) as well as enthalpy, entropy, and free energy values are obtained for pyran ring tautomerism exhibited by two Moco model complexes, namely, (Et4N)[Tp*Mo(O)(S2BMOPP)] (1) and (Et4N)[Tp*Mo(O)(S2PEOPP)] (2), as a solvent-dependent equilibrium process. Keq values obtained from (1)H NMR data in seven deuterated solvents show a correlation between solvent polarity and tautomer form, where solvents with higher polarity parameters favor the pyran form.

A series of molybdenum−pterin complexes produced from reactions of molybdenum and pterin reagents in various oxidation states has been investigated by X-ray photoelectron spectroscopy (XPS). Prior difficulties in making oxidation state assignments for the metal center and coordinated pterin can be resolved through comparison of Mo 3d binding energies (BE) for these new complexes with the BEs of standard molybdenum complexes. XPS analysis of molybdenum−pterin complexes produced from reactions of Mo(VI) reagents with tetrahydropterins show binding energies that are shifted by 1.5−1.8 eV to lower energies as compared to the BEs observed for the oxo-Mo(VI) reagents. The opposite shift in BE values is observed for complexes prepared from Mo(IV) chloride and fully oxidized pterins where BEs shift to higher values with respect to those for the starting Mo(IV) reagents. Remarkably, the BEs obtained for Mo−pterin complexes originating from Mo(VI)−tetrahydropterin reactions are nearly identical with those from Mo(I...

The coordination of alloxazine and pterins to molybdenum(IV) is demonstrated in this study. The synthesis of MoOCl3(pteridineH), where pteridineH is the protonated form of 1,3,7,8-tetramethylalloxazine (tmaz), 2-pivaloyl-6,7-dimethylpterin (piv-dmp), and 6,7-dimethylpterin (dmp), proceeds readily starting from Mo(IV)Cl4(acetonitrile)2 and the pteridine ligand in chloroform or methanol. X-ray crystal structures of MoOCl3(tmazH) (1) and MoOCl3(piv-dmpH) (2) show that Mo chelates each pteridine at the carbonyl oxygen and pyrazine nitrogen and that the pteridine ligand is protonated at the other nitrogen in the pyrazine ring. A third X-ray structure for MoOCl3(H3dmp) (4) is included in this work since its determination permits the comparison of metrical parameters for the oxidized and reduced forms of a pterin in identical molybdenum coordination environments. The major difference observed in the structures of 2 as compared to 4 is the Mo−N5 bond length which is significantly shorter in compound 4 containing ...

The synthesis and structure of a new molybdenum complex coordinated by a reduced pterin is reported. [MoOCl(detc)(H3dmp)]Cl (1) (where detc is diethyldithiocarbamate and H3dmp is 6,7-dimethyl-6,7,8-trihydropterin) is prepared from MoOCl2(detc)2 and H4dmp (6,7-dimethyl-5,6,7,8-tetrahydropterin). The X-ray structure determination of [MoOCl(detc)(H3dmp)]Cl·MeOH reveals an octahedral complex where the reduced pterin ligand coordinates through the carbonyl oxygen and pyrazine ring nitrogen atoms. An extensive hydrogen bonding network in the crystal lattice connects adjacent complexes, the chloride counterion, and the molecule of methanol. This hydrogen bonding persists in solution where it is identified by characteristic absorptions in the electronic spectrum. Dimethyl sulfoxide (DMSO) oxidizes [MoOCl(detc)(H3dmp)]Cl, producing 1 equiv of dimethylpterin and 1/2 equiv of oxidized dithiocarbamate, tetraethylthiuramdisulfide (TETDS), a reaction that constitutes a net five-electron oxidation of the molybdenum comp...

Syntheses and physical properties of pterin and pteridine complexes for first-row transition metals are described. Characterization used single-crystal x-ray diffraction, spectroscopic, and microanalytical methods. These data all indicate that pterin and pteridine ligands chelate via oxygen and nitrogen atoms. Three copper complexes have been structurally determined. Cu(tppb)(pterin) [tppb − =tris(3-phenylpyrazolyl)hydroborate] crystallizes in the triclinic space group P1

The preparation and characterization of new model complexes for the molybdenum cofactor are reported. The new models are distinctive for the inclusion of pterin-substituted dithiolene chelates and have the formulation Tp ∗ MoX(pterin-R-dithiolene) (Tp ∗ = tris(3,5,-dimethylpyrazolyl)borate), X = O, S, R = aryl. Syntheses of Mo(4+) and (5+) complexes of two pterin-dithiolene derivatives as both oxo and sulfido compounds, and improved syntheses for pterinyl alkynes and [Et 4 N][Tp ∗ Mo IV (S)S 4 ] reagents are described. Characterization methods include electrospray ionization mass spectrometry, electrochemistry, infrared spectroscopy, electron paramagnetic resonance and magnetic circular dichroism. Cyclic voltammetry reveals that the Mo(5+/4+) reduction potential is intermediate between that for dithiolenes with electron-withdrawing substituents and simple dithiolates chelates. Electron paramagnetic resonance and magnetic circular dichroism of Mo(5+) complexes where X = O, R = aryl indicates that the molybdenum environment in the new models is electronically similar to that in Tp ∗ MoO(benzenedithiolate).

Mo (CO) (PhC 2 H) (P Et 3 ) 2 Br 2 cristallise dans le systeme monoclinique, groupe d'espace P2 1/n et sa structure est affinee jusqu'a R=0,048

Caracterisation au moyen de la spectrometrie IR des complexes de cobalt (II). Etude radiocristallographique avec determination de la structure moleculaire

Ausgehend von den Hexacarbonylen (I) wird uber die Carbonyliodide (III) und (IV) wie aufgezeigt eine verbesserte Darstellungsmethode fur die Mo(II)- und W(II)-dithiocarbamate (VI) demonstriert.

The synthesis of a series of molybdenum dimers with bridging sulfur and alkyne ligands has been realized from monomeric Mo(R/sup 1/C==CR/sup 2/)/sub 2/(S/sub 2/CNR/sub 2/)/sub 2/ reagents (R/sup 1/ = H, R/sup 2/ = Ph; R/sup 1/ = CH/sub 3/, R/sup 2/ = Ph; R/sup 1/ = H, R/sup 2/ = n-Bu; R/sup 1/ = R/sup 2/ = Et). The molecular structure of the dimeric 3-hexyne derivative Mo/sub 2/(..mu..-S)(..mu..-EtC==CEt)(S/sub 2/CNMe/sub 2/) has been determined by a single-crystal X-ray diffraction study. Proton NMR spectra of the dimeric products indicate the presence of at least two isomers for symmetrical alkyne derivatives (RC==CR) and at least four isomers for unsymmetrical alkyne derivatives (RC==CR) in solution. The Mo-Mo distance of 2.647 angstrom observed in the 3-hexyne-bridged dimer suggests an attractive metal-metal interaction. A qualitative molecular orbital description has been formulated which accounts for the diamagnetism of these dimers and the observed structural parameters.

Ausgehend von den Hexacarbonylen (I) wird uber die Carbonyliodide (III) und (IV) wie aufgezeigt eine verbesserte Darstellungsmethode fur die Mo(II)- und W(II)-dithiocarbamate (VI) demonstriert.

Caracterisation au moyen de la spectrometrie IR des complexes de cobalt (II). Etude radiocristallographique avec determination de la structure moleculaire