Solvent coordination in gas-phase [Mn.(H(2)O)(n)](2+) and [Mn.(ROH)(n)](2+) complexes: theory and experiment

An experimental gas-phase study of the intensities and fragmentation patterns of [Mn.(H(2)O)(n)](2+) and [Mn.(ROH)(n)](2+) complexes shows the combinations [Mn.(H(2)O)(4)](2+) and [Mn.(ROH)(4)](2+) to be stable. Evidence in complexes involving the alcohols methanol, ethanol, 1-propanol, and 2-propanol favors preferential fragmentation to [Mn.(ROH)(4)](2+), whereas the fragmentation data for water is less clear. Supporting density functional calculations show that both [Mn.(H(2)O)(4)](2+) and [Mn.(MeOH)(4)](2+) adopt stable tetrahedral configurations, similar to those proposed for biochemical systems where solvent availability and coordination is restricted. Calculated incremental binding energies show a gradual decline on going from one to six solvent molecules, with a step occurring between four and five molecules. The addition of further solvent molecules to the stable [Mn.(MeOH)(4)](2+) unit shows a preference for [Mn.(MeOH)(4)(MeOH)(1,2)](2+) structures, where the extra molecules occupy hydrogen-bonded sites in the form of a secondary solvation shell. Very similar behavior is seen on the part of water. As part of an analysis of the experimental data, the calculations have explored the influence different spins states of Mn(2+) have on solvent geometry. It is concluded that the experimental observations are best reproduced when the central Mn(2+) ion is in the high-spin (6)S ground state. The results are also considered in terms of the biochemical activity of Mn(2+) where the ion is capable of isomorphous substitution with Zn(2+), which itself exhibits a preference for tetrahedral coordination.     

Ultrafast nonadiabatic dynamics of [Fe(II)(bpy)(3)](2+) in solution

The ultrafast relaxation of aqueous iron(II)-tris(bipyridine) upon excitation into the singlet metal-to-ligand charge-transfer band (1MLCT) has been characterized by femtosecond fluorescence up-conversion and transient absorption (TA) studies. The fluorescence experiment shows a very short-lived broad 1MLCT emission band at approximately 600 nm, which decays in < or =20 fs, and a weak emission at approximately 660 nm, which we attribute to the 3MLCT, populated by intersystem crossing (ISC) from the 1MLCT state. The TA studies show a short-lived (<150 fs) excited-state absorption (ESA) below 400 nm, and a longer-lived one above 550 nm, along with the ground-state bleach (GSB). We identify the short-lived ESA as being due to the 3MLCT state. The long-lived ESA decay and the GSB recovery occur on the time scale of the lowest excited high-spin quintet state 5T2 lifetime. A singular value decomposition and a global analysis of the TA data, based on a sequential relaxation model, reveal three characteristic time scales: 120 fs, 960 fs, and 665 ps. The first is the decay of the 3MLCT, the second is identified as the population time of the 5T2 state, while the third is its decay time to the ground state. The anomalously high ISC rate is identical in [RuII(bpy)3]2+ and is therefore independent of the spin-orbit constant of the metal atom. To reconcile these rates with the regular quasi-harmonic vibrational progression of the 1MLCT absorption, we propose a simple model of avoided crossings between singlet and triplet potential curves, induced by the strong spin-orbit interaction. The subsequent relaxation steps down to the 5T2 state dissipate approximately 2000 cm-1/100 fs. This rate is discussed, and we conclude that it nevertheless can be described by the Fermi golden rule, despite its high value.     

Spectral properties of polypyridyl ruthenium complexes intercalated in DNA: theoretical insights into the surrounding effects of [Ru(dppz)(bpy)(2)](2+)

The UV/Visible absorption properties of a polypyridyl ruthenium complex upon intercalation on DNA are studied at the mixed quantum mechanics molecular mechanics level of theory. Vertical excitation transitions are computed by time dependent density functional theory. Particular emphasis is put on the different levels at which the macromolecular environment is treated, and in particular on the analysis of the effect of mechanical, electrostatic and polarizable embedding. We show that with the highest level of theory the experimental absorption wavelengths are reproduced with a difference of only 2 or 3 nm for the low energy bands. The systematic analysis of the individual vertical transitions allows us to get much more insights into the role played by the environment, in particular, in metal to ligand and intra ligand charge transfer transitions that can lead to the production of DNA oxidative lesions exploitable in phototherapy.     

Built to order: molecular tinkertoys from the [Re(6)(mu(3)-Se)(8)](2+) clusters

Ligand substitution of [Re(6)(mu(3)-Se)(8)(PEt(3))(5)(CH(3)CN)](SbF(6))(2) (1) with pyridyl-based ligands, 2,4,6-tri-4-pyridyl-1,3,5-triazine (L1) and 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (L2), produced respectively the star-shaped tricluster (T1) and tetracluster (T2) arrays, wherein three (T1) and four (T2) units of the [Re(6)(mu(3)-Se)(8)](2+) core-containing clusters are interconnected by the corresponding bridging ligands. These novel supramolecular assemblies were characterized by a combination of NMR ((1)H and (31)P) spectroscopy, ESI-MS, and microanalysis. The molecular and solid-state structures of T1 have also been established by single-crystal X-ray diffraction.     

Preparation and Structures of the 2.2.2-Cryptand(1+) Salts of the [Sb(2)Se(4)](2)(-), [As(2)S(4)](2)(-), [As(10)S(3)](2)(-), and [As(4)Se(6)](2)(-) Anions

2.2.2-Cryptand(1+) salts of the [Sb(2)Se(4)](2)(-), [As(2)S(4)](2)(-), [As(10)S(3)](2)(-), and [As(4)Se(6)](2)(-) anions have been synthesized from the reduction of binary chalcogenide compounds by K in NH(3)(l) in the presence of the alkali-metal-encapsulating ligand 2.2.2-cryptand (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane), followed by recrystallization from CH(3)CN. The [Sb(2)Se(4)](2)(-) anion, which has crystallographically imposed symmetry 2, consists of two discrete edge-sharing SbSe(3) pyramids with terminal Se atoms cis to each other. The Sb-Se(t) bond distance is 2.443(1) ?, whereas the Sb-Se(b) distance is 2.615(1) ? (t = terminal; b = bridge). The Se(b)-Sb-Se(t) angles range from 104.78(4) to 105.18(5) degrees, whereas the Se(b)-Sb-Se(b) angles are 88.09(4) and 88.99(4) degrees. The (77)Se NMR data for this anion in solution are consistent with its X-ray structure (delta 337 and 124 ppm, 1:1 intensity, -30 degrees C, CH(3)CN/CD(3)CN). Similar to this [Sb(2)Se(4)](2)(-) anion, the [As(2)S(4)](2)(-) anion consists of two discrete edge-sharing AsS(3) pyramidal units. The As-S(t) bond distances are 2.136(7) and 2.120(7) ?, whereas the As-S(b) distances range from 2.306(7) to 2.325(7) ?. The S(b)-As-S(t) angles range from 106.2(3) to 108.2(3) degrees, and the S(b)-As-S(b) angles are 88.3(2) and 88.9(2) degrees. The [As(10)S(3)](2)(-) anion has an 11-atom As(10)S center composed of six five-membered edge-sharing rings. One of the three waist positions is occupied by a S atom, and the other two waist positions feature As atoms with exocyclic S atoms attached, making each As atom in the structure three-coordinate. The As-As bond distances range from 2.388(3) to 2.474(3) ?. The As-S(t) bond distances are 2.181(5) and 2.175(4) ?, and the As-S(b) bond distance is 2.284(6) ?. The [As(4)Se(6)](2)(-) anion features two AsSe(3) units joined by Se-Se bonds with the two exocyclic Se atoms trans to each other. The average As-Se(t) bond distance is 2.273(2) ?, whereas the As-Se(b) bond distances range from 2.357(3) to 2.462(2) ?. The Se(b)-As-Se(t) angles range from 101.52(8) to 105.95(9) degrees, and the Se(b)-As-Se(b) angles range from 91.82(7) to 102.97(9) degrees. The (77)Se NMR data for this anion in solution are consistent with its X-ray structure (delta 564 and 317 ppm, 3:1 intensity, 25 degrees C, DMF/CD(3)CN).     

Highly electrophilic, 16-electron [Ru(P(OMe)(OH)(2))(dppe)(2)](2+) complex turns H(2)(g) into a strong acid and splits a Si-H bond heterolytically. Synthesis and structure of the novel phosphorous acid complex [Ru(P(OH)(3))(dppe)(2)](2+)

The highly electrophilic, 16-electron, coordinatively unsaturated [Ru(P(OMe)(OH)(2))(dppe)(2)][OTf](2) complex brings about the heterolytic activation of H(2)(g) and spontaneously generates HOTf. In addition, trans-[Ru(H)(P(OMe)(OH)(2))(dppe)(2)](+) and an unprecedented example of a phosphorous acid complex, [Ru(P(OH)(3))(dppe)(2)](2+), are formed. The [Ru(P(OMe)(OH)(2))(dppe)(2)][OTf](2) complex also cleaves the Si-H bond in EtMe(2)SiH in a heterolytic fashion, resulting in the trans-[Ru(H)(P(OMe)(OH)(2))(dppe)(2)](+) derivative.     

Routes to metallodendrimers of the [Re(6)(mu(3)-Se)(8)](2+) core-containing clusters

The reaction of [Re6(mu3-Se)8(PEt3)5(MeCN)](SbF6)2 with an excess of 1,2-bis(4-pyridyl)ethane (L1) and (E)-1,2-bis(4-pyridyl)ethene (L2) produced [Re6(mu3-Se)8(PEt3)5(L1)](SbF6)2 and [Re6(mu3-Se)8(PEt3)5(L2)](SbF6)2, respectively, each bearing an accessible pyridyl N atom capable of further metal coordination. Reacting these cluster complex-based ligands with [Re6(mu3-Se)8(MeCN)6](SbF6)2 afforded two heptacluster metallodendrimers, each featuring a central [Re6(mu3-Se)8]2+ cluster core surrounded by six units of [Re6(mu3-Se)8(PEt3)5]2+ via the bridging interactions of its respective dipyridyl-based ligands. Their identity and stereochemistry have been established, with the most convincing evidence furnished by a unique 77Se NMR spectroscopic study. Electrochemical studies suggest very interesting electronic properties of these novel metallodendrimers.     

Spectroscopic and structural characterization of the [Fe(imidazole)(6)](2+) cation

Spectroscopic, structural, and magnetic data are presented for Fe(C(3)H(4)N(2))(6)(NO(3))(2), which facilitate a precise definition of the electronic and molecular structure of the [Fe(Im)(6)](2+) cation. The structure was determined at 120(1) K by X-ray diffraction methods. The salt crystallizes in the trigonal space group R3 with unit-cell parameters a = 12.4380(14) A, c = 14.5511(18) A, and Z = 3. All the imidazole ligands are equivalent with an Fe-N bond distance of 2.204(1) A. Variable-temperature inelastic neutron scattering (INS) measurements identify a cold magnetic transition at 19.4(2) cm(-1) and a hot transition at 75.7(6) cm(-1). The data are interpreted using a ligand field Hamiltonian acting in the weak-field (5)D basis, from which the diagonal trigonal field splitting of the (5)T(2g) (O(h)) term is estimated as approximately 485 cm(-1), with the (5)A(g) (S(6)) component lower lying. High-field multifrequency (HFMF) EPR data and measurements of the magnetic susceptibility are also reported and can be satisfactorily modeled using the energies and wave functions derived from analysis of the INS data. The electronic and molecular structures are related through angular overlap model calculations, treating the imidazole ligand as a weak pi-donor.     

The mechanism for water exchange in [UO(2)(H(2)O)(5)](2+) and [UO(2)(oxalate)(2)(H(2)O)](2-), as studied by quantum chemical methods.

The mechanisms for the exchange of water between [UO(2)(H(2)O)(5)](2+), [UO(2)(oxalate)(2)(H(2)O)](2)(-)(,) and water solvent along dissociative (D), associative (A) and interchange (I) pathways have been investigated with quantum chemical methods. The choice of exchange mechanism is based on the computed activation energy and the geometry of the identified transition states and intermediates. These quantities were calculated both in the gas phase and with a polarizable continuum model for the solvent. There is a significant and predictable difference between the activation energy of the gas phase and solvent models: the energy barrier for the D-mechanism increases in the solvent as compared to the gas phase, while it decreases for the A- and I-mechanisms. The calculated activation energy, Delta U(++), for the water exchange in [UO(2)(H(2)O)(5)](2+) is 74, 19, and 21 kJ/mol, respectively, for the D-, A-, and I-mechanisms in the solvent, as compared to the experimental value Delta H(++) = 26 +/- 1 kJ/mol. This indicates that the D-mechanism for this system can be ruled out. The energy barrier between the intermediates and the transition states is small, indicating a lifetime for the intermediate approximately 10(-10) s, making it very difficult to distinguish between the A- and I-mechanisms experimentally. There is no direct experimental information on the rate and mechanism of water exchange in [UO(2)(oxalate)(2)(H(2)O)](2-) containing two bidentate oxalate ions. The activation energy and the geometry of transition states and intermediates along the D-, A-, and I-pathways were calculated both in the gas phase and in a water solvent model, using a single-point MP2 calculation with the gas phase geometry. The activation energy, Delta U(++), in the solvent for the D-, A-, and I-mechanisms is 56, 12, and 53 kJ/mol, respectively. This indicates that the water exchange follows an associative reaction mechanism. The geometry of the A- and I-transition states for both [UO(2)(H(2)O)(5)](2+) and [UO(2)(oxalate)(2)(H(2)O)](2-) indicates that the entering/leaving water molecules are located outside the plane formed by the spectator ligands.     

Substitution reactions with [ReBr(2)(CO)(2)(NCCH(3))(2)](-): a convenient route to complexes with the cis-[Re(CO)(2)](+) core

Water- and air-stable complexes comprising the cis-[Re(CO)(2)](+) core can be synthesized from the (Et(4)N)[ReBr(2)(NCCH(3))(2)(CO)(2)] precursor . Complex showed distinctly different chemical and electronic behaviour compared to [ReBr(3)(CO)(3)](2-). Substituting the two bromides in with imidazole-like ligands or alpha,alpha'-diimines gave new complexes with potential applications in bioinorganic chemistry and photochemistry. The two acetonitrile ligands are very stably bound and could not be replaced. Under CO pressure, the uncommon complex mer-[ReBr(NCCH(3))(2)(CO)(3)] was formed from . The reaction of with the tetradentate ligand bis(2-pyridylmethyl)glycine (BPG) finally induced a four fold substitution at the metal center to form a [Re(CO)(2)(L(4))](+)-type complex.     

Redox chemistry of morpholine-based Os(VI)-hydrazido complexes: trans-[Os(VI)(tpy)(Cl)2(NN(CH2)4O)](2+)

The oxidations of benzyl alcohol, PPh3, and the sulfides (SEt2 and SPh2) (Ph = phenyl and Et = ethyl) by the Os(VI)-hydrazido complex trans-[Os(VI)(tpy)(Cl)2(NN(CH2)4O)](2+) (tpy = 2,2':6',2' '-terpyridine and O(CH2)4N(-) = morpholide) have been investigated in CH3CN solution by UV-visible monitoring and product analysis by gas chromatography-mass spectrometry. For benzyl alcohol and the sulfides, the rate law for the formation of the Os(V)-hydrazido complex, trans-[Os(V)(tpy)(Cl)2(NN(CH2)4O)](+), is first order in both trans-[Os(VI)(tpy)(Cl)2(NN(CH2)4O)](2+) and reductant, with k(benzyl) (25.0 +/- 0.1 degrees C, CH3CN) = (1.80 +/- 0.07) x 10(-4) M(-1) s(-1), k(SEt2) = (1.33 +/- 0.02) x 10(-1) M(-1) s(-1), and k(SPh2) = (1.12 +/- 0.05) x 10(-1) M(-1) s(-1). Reduction of trans-[Os(VI)(tpy)(Cl)2(NN(CH2)4O)](2+) by PPh3 is rapid and accompanied by isomerization and solvolysis to give the Os(IV)-hydrazido product, cis-[Os(IV)(tpy)(NCCH3)2(NN(CH2)4O)](2+), and OPPh3. This reaction presumably occurs by net double Cl-atom transfer to PPh3 to give Cl2PPh3 that subsequently undergoes hydrolysis by trace H2O to give the final product, OPPh3. In the X-ray crystal structure of the Os(IV)-hydrazido complex, the Os-N-N angle of 130.9(5) degrees and the Os-N bond length of 1.971(7) A are consistent with an Os-N double bond.     

Single-walled carbon nanotube growth using [Fe(3)(mu(3)-O)(mu-O(2)CR)(6)(L)(3)](n+) complexes as catalyst precursors

We present herein the VLS growth of SWNTs from oxo-hexacarboxylate-triron precursors, [Fe(3)O(O(2)CCH(3))(6)(EtOH)(3)] and [Fe(3)O(O(2)CCH(2)OMe)(6)(H(2)O)(3)][FeCl(4)], on spin-on-glass surfaces, using C(2)H(4)/H(2) (750 degrees C) and CH(4)/H(2) (800 and 900 degrees C) growth conditions. The SWNTs have been characterized by AFM, SEM and Raman spectroscopy. The characteristics of the SWNTs are found to be independent of the identity of the precursor complex or the solvent from which it is spin-coated. The as grown SWNTs show a low level of side-wall defects and have an average diameter of 1.2-1.4 nm with a narrow distribution of diameters. At 750 and 800 degrees C the SWNTs are grown with a range of lengths (300 nm-9 microm), but at 900 degrees C only the longer SWNTs are observed (6-8 microm). The yield of SWNTs per unit area of catalyst nanoparticle decreases with the growth temperature. We have demonstrated that spin coating of molecular precursors allows for the formation of catalyst nanoparticles suitable for growth of SWNTs with a high degree of uniformity in the diameter, without the formation of preformed clusters of a set diameter.     

Solid-state ligand dynamics in interpenetrating Mn[N(CN)(2)](2)(pyrazine): a neutron spectroscopy study

We have used quasielastic neutron scattering to probe the solid-state ligand dynamics in the coordination polymer Mn[N(CN)(2)](2)(pyz) [pyz = pyrazine] which has double-interpenetrating 3D lattices. A reversible structural phase transition occurs at 410 K as shown by neutron spectroscopy and differential scanning calorimetry. The origin of this transition is linked to rotational dynamics associated with the bridging pyz ligands. At 425 K, the pyrazine ring motion can be solely regarded as a 180 degrees reorientational jump about the axis defined by the Mn-N coordinative bonds, occurring with a correlation time of approximately 70 ps. This model can be extended to the 200-410 K temperature region using high-resolution backscattering spectroscopy to measure an identical motion on the time scale of nanoseconds with an activation energy of 24 +/- 2 kJ mol(-1). In contrast, no quasielastic scattering is seen for the 2D layered variant beta-Cu[N(CN)(2)](2)(pyz), owing to its more compact layer packing motif. Importantly, this work represents the very first study of solid-state rotational dynamics in an interpenetrating lattice structure.     

Unimolecular reactivity of uracil-Cu(2+) complexes in the gas phase.

The gas-phase interaction of copper(II) ions with uracil are studied by means of mass spectrometry and B3LYP/6-311+G(2df,2p)//B3LYP/6-31G(d) calculations. Positive-ion electrospray spectra show that the reaction of uracil with copper(II) gives rise to singly charged species, whereby the [Cu(uracil--H)](+) complex is the most intense ion in the spectra at low concentration. Mass spectrometry/mass spectrometry (MS/MS) experiments show that the loss of HNCO and NCO are the dominant fragmentation processes, accompanied by a minor loss of CO. A systematic study of the spectra obtained with different labeled species, namely, 2-(13)C- (m/z 175), 2-(13)C,1,3-(15)N(2)- (m/z 177) and 3-(15)N-uracil (m/z 175), concludes unambiguously that both the loss of HNCO and NCO involve exclusively C2 and N3, whereas only C4 is involved in the loss of CO. Suitable mechanisms for these fragmentation processes are proposed through a theoretical survey of the corresponding potential energy surface. In these mechanisms, pi complexes, which lie high in energy with respect to the global minimum, play a significant role in the loss of NCO; this explains why both products, HNCO and NCO involve the same atoms of the ring.     

Reactions of [Ru(H(2)O)(6)](2+) with water-soluble tertiary phosphines

In aqueous solutions under mild conditions, [Ru(H(2)O)(6)](2+) was reacted with various water-soluble tertiary phosphines. As determined by multinuclear NMR spectroscopy, reactions with the sulfonated arylphosphines L =mtppms, ptppms and mtppts yielded only the mono- and bisphosphine complexes, [Ru(H(2)O)(5)L](2+), cis-[Ru(H(2)O)(4)L(2)](2+), and trans-[Ru(H(2)O)(4)L(2)](2+) even in a high ligand excess. With the small aliphatic phosphine L = 1,3,5-triaza-7-phosphatricyclo-[3.3.1.1(3,7)]decane (pta) at [L]:[Ru]= 12:1, the tris- and tetrakisphosphino species, [Ru(H(2)O)(3)(pta)(3)](2+), [Ru(H(2)O)(2)(pta)(4)](2+), [Ru(H(2)O)(OH)(pta)(4)](+), and [Ru(OH)(2)(pta)(4)] were also detected, albeit in minor quantities. These results have significance for the in situ preparation of Ru(II)-tertiary phosphine catalysts. The structures of the complexes trans-[Ru(H(2)O)(4)(ptaMe)(2)](tos)(4)x2H(2)O, trans-[Ru(H(2)O)(4)(ptaH)(2)](tos)(4)[middle dot]2H(2)O, and trans-mer-[RuI(2)(H(2)O)(ptaMe)(3)]I(3)x2H(2)O, containing protonated or methylated pta ligands (ptaH and ptaMe, respectively) were determined by single crystal X-ray diffraction.     

Ge(7)O(13)(OH)(2)F(3)](3)(-).Cl(-).2[Ni(dien)(2)](2+): the first chainlike germanate templated by a transition metal complex

The first chainlike germanate, [Ge(7)O(13)(OH)(2)F(3)](3)(-).Cl(-).2[Ni(dien)(2)](2+), has been solvothermally synthesized by using Ni(dien)(2)(2+) cations as the template and characterized by IR, SEM, TGA, powder X-ray diffraction (PXRD), energy-dispersive X-ray analysis (EDXA), elemental analysis, and single-crystal X-ray diffraction, respectively. This compound crystallized in the monoclinic space group P2/nwith a = 8.8904(2) A, b = 17.4374(3) A, c = 13.2110(3) A, beta = 101.352(1) degrees, V = 2007.97(7) A(3), and Z = 2. Interestingly, the structure contains two types of chiral mer-[Ni(dien)(2)](2+) cations and two types of chiral chains, one left-handed and the other right-handed, which lead to a racemic compound. The orderly separation of achiral s-fac-[Ni(dien)(2)](2+) and chiral mer-[Ni(dien)(2)](2+) isomers was found in the structure. The structure is stabilized by N-H.O(F, Cl) hydrogen bonds.     

State-resolved UV photofragmentation spectrum of the metal dication complex [Zn(pyridine)(4)](2+)

A combined theoretical and experimental study of electronic transitions in the complex [Zn(pyridine)(4)](2+) provides the first example of a state-resolved electronic spectrum to be recorded for a dication complex in the gas phase.     

A mechanistic study of the samarium(II)-mediated reduction of aryl nitro compounds to the corresponding crylamines. The crystal structures of [Sm[N(SiMe(3))(2)](2)(thf)](2)(mu(2)-O) and [(Me(3)Si)(2)N](2)Sm(thf)(mu-PhNNPh)Sm[N(SiMe(3))(2)](2)

Treatment of nitrobenzene and other various nitroarenes with 6 equiv of samarium(II) under strictly anhydrous conditions allows for the isolation of aniline or the corresponding arylamine. Reducing the number of samarium(II) equivalents allows for the isolation of intermediate species, e.g., azoarenes or hydrazines. Use of Sm[N(SiMe(3))(2)](2), in place of the typically used SmI(2), has allowed for the detailed examination of the aqueous and nonaqueous species formed in this reduction and has been instrumental in delineation of the stepwise reaction mechanism. This is the first time that the reaction intermediates of an organic reaction mediated by samarium(II) have been isolated and analyzed by (1)H NMR and X-ray crystallography.     

Synthesis and properties of [Ru(2)(acac)(4)(bptz)](n+) (n=0,1) and crystal structure of [Ru(2)(acac)(4)(bptz)

The neutral complex [Ru(2)(acac)(4)(bptz)] (I) has been prepared by the reaction of Ru(acac)(2)(CH(3)CN)(2) with bptz (bptz = 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine) in acetone. The diruthenium(II,II) complex (I) is green and exhibits an intense metal-ligand charge-transfer band at 700 nm. Complex I is diamagnetic and has been characterized by NMR, optical spectroscopy, IR, and single-crystal X-ray diffraction. Crystal structure data for I are as follows: triclinic, P1, a = 11.709(2) A, b = 13.487(3) A, c = 15.151(3) A, alpha = 65.701(14) degrees, beta = 70.610(14) degrees, gamma = 75.50(2) degrees, V = 2038.8(6) A(3), Z = 2, R = 0.0610, for 4397 reflections with F(o) > 4sigmaF(o). Complex I shows reversible Ru(2)(II,II)-Ru(2)(II,III) and Ru(2)(II,III)-Ru(2)(III,III) couples at 0.17 and 0.97 V, respectively; the 800 mV separation indicates considerable stabilization of the mixed-valence species (K(com) > 10(13)). The diruthenium(II,III) complex, [Ru(2)(acac)(4)(bptz)](PF(6)) (II) is prepared quantitatively by one-electron oxidation of I with cerium(IV) ammonium nitrate in methanol followed by precipitation with NH(4)PF(6). Complex II is blue and shows an intense MLCT band at 575 nm and a weak band at 1220 nm in CHCl(3), which is assigned as the intervalence CT band. The mixed valence complex is paramagnetic, and an isotropic EPR signal at g = 2.17 is observed at 77 and 4 K. The solvent independence and narrowness of the 1200 nm band show that complex II is a Robin and Day class III mixed-valence complex.