Spectro- and electrochemical studies of some ruthenium and osmium complexes of 2-(2'-pyridyl)benzimidazole; complexes with intra-molecular charge transfer

Reaction of Ru3(CO)12, with 2-(2'-pyridyl)benzimidazole (HPBI) resulted in the formation of Ru(CO)3(HPBI) (I) complex. In presence of pyridine or dipyridine, the two derivatives [Ru(CO)3(HPBI)].Py (II) and [Ru(CO)3(HPBI)].dpy (III) were isolated. The corresponding reactions of Os3(CO)12 yielded only one single product; Os(CO)2(HPBI)2 (IV). Spectroscopic studies of these complexes revealed intramolecular metal to ligand CT interactions. Reactions of RuCl3 with HPBI gave three distinct products; [Ru(HPBI)2Cl2]Cl (V), [Ru(HPBI)(dipy)Cl2]C1 (VI) and [Ru(PBI)2(py)2]Cl (VII). The UV-vis studies indicated the presence of intramolecular ligand to metal CT interactions. Electrochemical investigation of the complexes showed some irreversible, reversible and quasi-reversible redox reactions due to tautomeric interconversions through electron transfer.     

（CH3）3NO存在下M（CO）5（M＋Fe,Ru,Os）的CO取代反应动力学研究

在(CH_3)_3NO存在下,PPh_3取代M(CO)_5(M=Fe,Ru,Os)中CO的反应速度遵循二级速度定律,分别与[M(CO)_5]和[(CH_3)_3NO]的一次方成正比,与[PPh_3]无关。反应速度按FeRu>Os的次序约减小4倍。 1 实验方法 典型的动力学实验中,将(CH_3)_3NO的C_2H_5OH溶液和PPh_3的己烷溶液分别用注射器加到体积合适的烧瓶中,再注入Fe(CO)_5并迅速震荡烧瓶,再取出一部分反应液立即注入充N_2     

Multiple additions of phenylgermanium ligands to tetraruthenium and tetraosmium carbonyl cluster complexes

Three new compounds, Ru4(mu4-GePh)2(mu-GePh2)2(mu-CO)2(CO)8 (11), Ru4(mu4-GePh)2(mu-GePh2)3(mu-CO)(CO)8 (12), and Ru4(mu4-GePh)2(mu-GePh2)4(CO)8 (13), were obtained from the reaction of H(4)Ru(4)(CO)12 with excess Ph(3)GeH in octane (11 and 12) or decane (13) reflux. Compound 11 was converted to compound 13 by reaction with Ph(3)GeH by heating solutions in nonane solvent to reflux. Compounds 11-13 each contain a square-type arrangement of four Ru atoms capped on each side by a quadruply bridging GePh ligand to form an octahedral geometry for the Ru(4)Ge(2) group. Compound 11 also contains two edge-bridging GePh(2) groups on opposite sides of the cluster and two bridging carbonyl ligands. Compound 12 contains three edge-bridging GePh(2) groups and one bridging carbonyl ligand. Compound 13 contains four bridging GePh(2) groups, one on each edge of the Ru4 square. The reaction of H(4)Os(4)(CO)12 with excess Ph(3)GeH in decane at reflux yielded two new tetraosmium cluster complexes, Os4(mu4-GePh)2(mu-GePh2)3(mu-CO)(CO)8 (14) and Os4(mu4-GePh)2(mu-GePh(2))4(CO)8 (15). These compounds are structurally similar to compounds 12 and 13, respectively.     

Electronic energy transfer and collection in luminescent molecular rods containing ruthenium(II) and osmium(II) 2,2':6',2"-terpyridine complexes linked by thiophene-2,5-diyl spacers

The electronic absorption spectra, luminescence spectra and lifetimes (in MeCN at room temperature and in frozen n-C3H7CN at 77 K), and electrochemical potentials (in MeCN) of the novel dinuclear [(tpy)Ru(3)Os(tpy)]4+ and trinuclear [(tpy)Ru(3)Os(3)Ru(tpy)]6- complexes (3 = 2,5-bis(2,2':6',2'-terpyridin-4-yl)thiophene) have been obtained and are compared with those of model mononuclear complexes and homometallic [(tpy)Ru(3)Ru(tpy)]4+, [(tpy)Os(3)Os(tpy)]4+ and [(tpy)Ru(3)Ru(3)Ru(tpy)]6+ Complexes. The bridging ligand 3 is nearly planar in the complexes, as seen from a preliminary X-ray determination of [(tpy)Ru(3)Ru(tpy)][PF6]4, and confers a high degree of rigidity upon the polynuclear species. The trinuclear species are rod-shaped with a distance of about 3 nm between the terminal metal centres. For the polynuclear complexes, the spectroscopic and electrochemical data are in accord with a significant intermetal interaction. All of the complexes are luminescent (phi in the range 10(-4)-10(-2) and tau in the range 6-340 ns, at room temperature), and ruthenium- or osmium-based luminescence properties can be identified. Due to the excited state properties of the various components and to the geometric and electronic properties of the bridge, Ru --> Os directional transfer of excitation energy takes place in the complexes [(tpy)Ru(3)Os(tpy)]4+ (end-to-end) and [(tpy)Ru(3)Os(3)Ru(tpy)]6+ (periphery-to-centre). With respect to the homometallic case, for [(tpy)Ru(3)Os(3)Ru(tpy)]6+ excitation trapping at the central position is accompanied by a fivefold enhancement of luminescence intensity.     

金属羰基化合物的结构对氧原子转移反应速率的影响

本文研究了氧化三甲胺Ｍｅ３ＮＯ与羰基簇合物Ｍ４（ＣＯ）１２－ｎＬｎ（Ｍ＝Ｃｏ，Ｉｒ；ｎ＝１，２；Ｌ＝磷配体）的氧转移反应动力学，讨论了反应机理。反应符合二级速率方程：ｒ＝Ｋ２［Ｍｅ３ＮＯ］［Ｍ４（ＣＯ）１２－ｎＬｎ］Ｍ４（ＣＯ）１２－ｎＬｎ的氧转移反应活性呈现如下顺序：中心元素不同时Ｃｏ４（ＣＯ）１２－ｎＬｎ＜Ｉｒ４（ＣＯ）１２－ｎＬｎ；取代配体不同时Ｍ４（ＣＯ）１２－ｎ（Ｐ（ＯＭｅ）３）ｎ＞Ｍ４     

Coordination chemistry of new ruthenium and osmium dihydroxyquinoxaline complexes

Trinuclear clusters M3(CO)12(M=Ru and Os) react with 2,3-dihydroxyquinoxaline (DQ) to give M(CO)2 (DQ) (DMSO) products. I.r. and n.m.r. spectroscopy show these complexes are trigonal bipyramidal with the two CO molecules differently bonded to the metal center; axially in the ruthenium complex and equatorially in the osmium complex. Prolonged heating of ruthenium(III) chloride with DQ gave the [Ru(DQ) (DMSO)3]Cl3 complex, the i.r. spectrum of which showed that the ligand is bonded to the metal in the catecholate form.     

Mononuclear and dinuclear complexes of dibenzoeilatin: synthesis, structure, and electrochemical and photophysical properties

This work describes a study of Ru(II) and Os(II) polypyridyl complexes of the symmetrical, fused-aromatic bridging ligand dibenzoeilatin (1). The synthesis, purification, and structural characterization by NMR of the mononuclear complexes [Ru(bpy)(2)(dbneil)](2+) (2), [Ru(tmbpy)(2)(dbneil)](2+) (3), and [Os(bpy)(2)(dbneil)](2+) (4), the homodinuclear complexes [[Ru(bpy)(2)](2)[micro-dbneil]](4+) (5), [[Ru(tmbpy)(2)](2)[micro-dbneil]](4+) (6), and [[Os(bpy)(2)](2)[micro-dbneil]](4+) (7), and the heterodinuclear complex [[Ru(bpy)(2)][micro-dbneil][Os(bpy)(2)]](4+) (8) are described, along with the crystal structures of 4, 6, and 7. Absorption spectra of the mononuclear complexes feature a low-lying MLCT band around 600 nm. The coordination of a second metal fragment results in a dramatic red shift of the MLCT band to beyond 700 nm. Cyclic and square wave voltammograms of the mononuclear complexes exhibit one reversible metal-based oxidation, as well as several ligand-based reduction waves. The first two reductions, attributed to reduction of the dibenzoeilatin ligand, are substantially anodically shifted compared to [M(bpy)(3)](2+) (M = Ru, Os), consistent with the low-lying pi orbital of dibenzoeilatin. The dinuclear complexes exhibit two reversible, well-resolved, metal-centered oxidation waves, despite the chemical equivalence of the two metal centers, indicating a significant metal-metal interaction mediated by the conjugated dibenzoeilatin ligand. Luminescence spectra, quantum yield, and lifetime measurements at room temperature in argon-purged acetonitrile have shown that the complexes exhibit (3)MLCT emission, which occurs in the IR-region between 950 and 1300 nm. The heterodinuclear complex 8 exhibits luminescence only from the Ru-based fragment, the intensity of which is less than 1% of that observed in the corresponding homodinuclear complex 5; no emission from the Os-based unit is observed, and an intramolecular quenching constant of k(q) > or = 3 x10(9) s(-)(1) is evaluated. The nature of the quenching process is briefly discussed.     

Osmium Complexes Useful in the Preparation of Metal Thin Film and Highly Efficient Electroluminescent Devices

Treatment of β-diketone ligand, such as hfacH (hexafluoroacetylacetone), with Os3(CO)12 in a stainless steel autoclave at elevated temperature afforded the corresponding mononuclear osmium complex [Os(CO)3(hfac)(tfa)] (1) in good yield. This complex is highly volatile and displays moderate stability at the higher temperatures; thus, it can be utilized for depositing metal thin-film material with overall quality comparable or better than those deposited using the commercially available chemical reagents. Moreover, combination of Os3(CO)12 with another class of chelate ligand such as 3-trifluoromethyl-5-(2-pyridyl) pyrazole (ppz)H gave formation of the Os(H) dicarbonyl complex [Os(CO)2(ppz)2] (2). This osmium complex shows blue phosphorescence at room temperature, which is characteristic for the 3ππ* emission with vibronic progressions at 430,457 and 480 nm. The remarkable photophysical properties were rationalized by a combination of π electron accepting CO ligand, relative ppz orientation and heavy-atom enhanced spin-orbit coupling effects. Related chemical transformations that afforded other useful luminescent Os complexes are presented.     

Ruthenium and osmium carbonyl clusters incorporating stannylene and stannyl ligands

The reaction of [Ru(3)(CO)(12)] with Ph(3)SnSPh in refluxing benzene furnished the bimetallic Ru-Sn compound [Ru(3)(CO)(8)(mu-SPh)(2)(mu(3)-SnPh(2))(SnPh(3))(2)] which consists of a SnPh(2) stannylene bonded to three Ru atoms to give a planar tetra-metal core, with two peripheral SnPh(3) ligands. The stannylene ligand forms a very short bond to one Ru atom [Sn-Ru 2.538(1) A] and very long bonds to the other two [Sn-Ru 3.074(1) A]. The germanium compound [Ru(3)(CO)(8)(mu-SPh)(2)(mu(3)-GePh(2))(GePh(3))(2)] was obtained from the reaction of [Ru(3)(CO)(12)] with Ph(3)GeSPh and has a similar structure to that of as evidenced by spectroscopic data. Treatment of [Os(3)(CO)(10)(MeCN)(2)] with Ph(3)SnSPh in refluxing benzene yielded the bimetallic Os-Sn compound [Os(3)(CO)(9)(mu-SPh)(mu(3)-SnPh(2))(MeCN)(eta(1)-C(6)H(5))] . Cluster has a superficially similar planar metal core, but with a different bonding mode with respect to that of . The Ph(2)Sn group is bonded most closely to Os(2) and Os(3) [2.786 and 2.748 A respectively] with a significantly longer bond to Os(1), 2.998 A indicating a weak back-donation to the Sn. The reaction of the bridging dppm compound [Ru(3)(CO)(10)(mu-dppm)] with Ph(3)SnSPh afforded [Ru(3)(CO)(6)(mu-dppm)(mu(3)-S)(mu(3)-SPh)(SnPh(3))] . Compound contains an open triangle of Ru atoms simultaneously capped by a sulfido and a PhS ligand on opposite sides of the cluster with a dppm ligand bridging one of the Ru-Ru edges and a Ph(3)Sn group occupying an axial position on the Ru atom not bridged by the dppm ligand.     

Triruthenium and triosmium carbonyl clusters containing chiral bidentate NHC-thiolate ligands derived from levamisole

The trinuclear complexes [M3(mu-Cl)(mu-S approximately CH)(CO)9] (M=Ru, Os; S approximately CH=1-ethylenethiolate-3-H-4-(S)-phenylimidazolin-2-ylidene) and [M3(mu-H)(mu-S approximately CMe)(CO)9] (M=Ru, Os; S approximately CMe=1-ethylenethiolate-3-methyl-4-(S)-phenylimidazolin-2-ylidene) have been prepared by treating [Ru3(CO)12] and [Os3(CO)10(MeCN)2] with levamisolium chloride or [M3(mu-H)(CO)11]- with methyl levamisolium triflate, respectively. The chiral N-heterocyclic carbene-thiolate ligands S approximately CH and S approximately CMe arise from the oxidative addition of the C-S bond of levamisolium or methyl levamisolium cations to anionic trinuclear clusters.     

Synthesis of the phosphino-fullerene PPh2(o-C6H4)(CH2NMeCH)C60 and its function as an η1-P or η3-P,C2 ligand

Following the method of Prato et al., reaction of C(60), N-methylglycine and o-(diphenylphosphino)benzaldehyde affords PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60) (1) in moderate yield. Compound 1 reacts with W(CO)(4)(NCMe)(2) to produce W(CO)(4)(η(3)-PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (2), through coordination of the phosphine group and one 6 : 6-ring junction of fullerene. Reaction of 1 and Os(3)(CO)(11)(NCMe) affords Os(3)(CO)(11)(PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (3), which undergoes a cluster fragmentation reaction in refluxing toluene to produce Os(CO)(3)(η(3)-PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (4). Thermal reaction of 1 and Os(3)(CO)(12) affords 3 and 4. On the other hand, reaction of 1 and Ru(3)(CO)(12) yields only the mononuclear complex Ru(CO)(3)(η(3)-PPh(2)(o-C(6)H(4))(CH(2)NMeCH)C(60)) (5). The structures of 1-3 and 5 were determined by an X-ray diffraction study.     

An alternative synthesis method for [Os(NN)(CO)(2)X(2)] complexes (NN = 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine; X = Cl, Br, I). Electrochemical and photochemical properties and behavior

A novel synthesis method is introduced for the preparation of [Os(NN)(CO)(2)X(2)] complexes (X = Cl, Br, I, and NN = 2,2'-bipyridine (bpy) or 4,4'-dimethyl-2,2'-bipyridine (dmbpy)). In the first step of this two-step synthesis, OsCl(3) is reduced in the presence of a sacrificial metal surface in an alcohol solution. The reduction reaction produces a mixture of trinuclear mixed metal complexes, which after the addition of bpy or dmbpy produce a trans(Cl)-[Os(NN)(CO)(2)Cl(2)] complex with a good 60-70% yield. The halide exchange of [Os(bpy)(CO)(2)Cl(2)] has been performed in a concentrated halidic acid (HI or HBr) solution in an autoclave, producing 30-50% of the corresponding complex. All of the synthesized trans(X)-[Os(bpy)(CO)(2)X(2)] (X = Cl, Br, I) complexes displayed a similar basic electrochemical behavior to that found in the ruthenium analog trans(Cl)-[Ru(bpy)(CO)(2)Cl(2)] studied previously, including the formation of an electroactive polymer [Os(bpy)(CO)(2)](n) during the two-electron electrochemical reduction. The absorption and emission properties of the osmium complexes were also studied. Compared to the ruthenium analogues, these osmium complexes display pronounced photoluminescence properties. The DFT calculations were made in order to determine the HOMO-LUMO gaps and to analyze the contribution of the individual osmium d-orbitals and halogen p-orbitals to the frontier orbitals of the molecules. The electrochemical and photochemical induced substitution reactions of carbonyl with the solvent molecule are also discussed.     

Mononuclear and dinuclear complexes of isoeilatin

This work describes the synthesis and characterization of mononuclear and dinuclear Ru(II) and Os(II) complexes based on the symmetrical bridging ligand isoeilatin (1). The crystal structure of 1.[HCl]2 consists of layers of tightly pi-stacked molecules of the biprotonated isoeilatin. The mononuclear complexes [Ru(bpy)2(ieil)]2+ (2(2+)) and [Os(bpy)2(ieil)]2+ (3(2+)) form discrete dimers in solution held together by face-selective pi-stacking interactions via the isoeilatin ligand. Coordination of a second metal fragment does not hinder the pi-stacking completely, as demonstrated by the concentration dependence of the 1H NMR spectra of the dinuclear complexes [{Ru(bpy)2}2{mu-ieil}]4+ (4(4+)), [{Os(bpy)2}2{mu-ieil}]4+ (5(4+)), and [{Ru(bpy)2}{mu-ieil}{Os(bpy)2}]4+ (6(4+)) and supported by the solid-state structure of meso-4.[Cl]4. The bridging isoeilatin ligand conserves its planarity even upon coordination of a second metal fragment, as demonstrated in the solid-state structures of meso-4.[Cl]4, meso-4.[PF6]4, and meso-5.[PF6]4. All of the dinuclear complexes exhibit a preference (3/2-3/1) for the formation of the heterochiral as opposed to the homochiral diastereoisomer. Absorption spectra of the mononuclear complexes feature a low-lying dpi(M) --> pi*iel MLCT band around 600 nm that shifts to beyond 700 nm upon coordination of a second metal fragment. Cyclic and square-wave voltammetry measurements of the complexes exhibit two isoeilatin-based reduction waves that are substantially anodically shifted compared to [M(bpy)3]2+ (M = Ru, Os). Luminescence spectra, quantum yields, and lifetime measurements at room temperature and at 77 K demonstrate that the complexes exhibit 3MLCT emission that occurs in the IR region between 950 and 1300 nm. Both the electrochemical and photophysical data are consistent with the low-lying pi orbital of the isoeilatin ligand. The dinuclear complexes exhibit two reversible, well-resolved, metal-centered oxidation waves, despite the chemical equivalence of the two metal centers, indicating a significant metal-metal interaction mediated by the bridging isoeilatin ligand.     

Spectroscopic and electrochemical studies of ruthenium and osmium complexes of salicylideneimine-2-thiophenol Schiff base

The reactions between [M(3)(CO)(12)], M = Ru and Os, and salicylideneimine-2-thiophenol Schiff base in THF under reflux gave [Ru(CO)(4)(satpH)] and [Os(CO)(3)(satpH(2))] complexes. Structures of the two complexes were proposed on the basis of spectroscopic studies. Magnetic study of [Ru(CO)(4)(satpH)] suggested that a change in oxidation state of the ruthenium atom from zero to +1 was achieved via oxidative addition of the SH group with a proton displacement to give a low-spin d(7) electronic configuration. UV-Vis spectra of the two complexes in different solvents exhibited visible bands due to metal-to-ligand charge transfer. Electrochemical investigation of the free ligand and complexes showed some cathodic and anodic irreversible peaks due to interconversions through electron transfer.     

Tuning the excited-state properties of [M(SnR3)2(CO)2(alpha-diimine)] (M = Ru, Os; R = Me, Ph)

The influences of R, the alpha-diimine, and the transition metal M on the excited-state properties of the complexes [M(SnR3)2(CO)2(alpha-diimine)] (M = Ru, Os; R = Ph, Me) have been investigated. Various synthetic routes were used to prepare the complexes, which all possess an intense sigma-bond-to-ligand charge-transfer transition in the visible region between a sigma(Sn-M-Sn) and a pi*(alpha-diimine) orbital. The resonance Raman spectra show that many bonds are only weakly affected by this transition. The room-temperature time-resolved absorption spectra of [M(SnR3)2(CO)2(dmb)] (M = Ru, Os; R = Me, Ph; dmb = 4,4'-dimethyl-2,2'-bipyridine) show the absorptions of the radical anion of dmb, in line with the SBLCT character of the lowest excited state. The excited-state lifetimes at room temperature vary between 0.5 and 3.6 microseconds and are mainly determined by the photolability of the complexes. All complexes are photostable in a glass at 80 K, under which conditions they emit with very long lifetimes. The extremely long emission lifetimes (e.g., tau = 1.1 ms for [Ru(SnPh3)2(CO)2(dmb)]) are about a thousand times longer than those of the 3MLCT states of the [Ru(Cl)(Me)(CO)2(alpha-diimine)] complexes. This is due to the weak distortion of the former complexes in their 3SBLCT states as seen from the very small Stokes shifts. Remarkably, replacement of Ru by Os hardly influences the absorption and emission energies of these complexes; yet the emission lifetime is shortened because of an increase of spin-orbit coupling. The quantum yield of emission at 80 K is 1-5% for these complexes, which is lower than might be expected on the basis of their slow nonradiative decay.     

Sigma-organyl complexes of ruthenium and osmium supported by a mixed-donor ligand

A series of vinyl, aryl, acetylide and silyl complexes [Ru(R)(kappa2-MI)(CO)(PPh3)2] (R = CH=CH2, CH=CHPh, CH=CHC6H4CH3-4, CH=CH(t)Bu, CH=2OH, C(C triple bond CPh)=CHPh, C6H5, C triple bond CPh, SiMe2OEt; MI = 1-methylimidazole-2-thiolate) were prepared from either [Ru(R)Cl(CO)(PPh3)2] or [Ru(R)Cl(CO)(BTD)(PPh3)2](BTD = 2,1,3-benzothiadiazole) by reaction with the nitrogen-sulfur mixed-donor ligand, 1-methyl-2-mercaptoimidazole (HMI), in the presence of base. In the same manner, [Os(CH=CHPh)(kappa2-MI)(CO)(PPh3)2] was prepared from [Os(CH=CHPh)(CO)Cl(BTD)(PPh3)2]. The in situ hydroruthenation of 1-ethynylcyclohexan-1-ol by [RuH(CO)Cl(BTD)(PPh3)2] and subsequent addition of the HMI ligand and excess sodium methoxide yielded the dehydrated 1,3-dienyl complex [Ru(CH=CHC6H9)(kappa2-MI)(CO)(PPh3)2]. Dehydration of the complex [Ru(CH=CHCPh2OH)(kappa2-MI)(CO)(PPh3)2] with HBF4 yielded the vinyl carbene [Ru(=CHCH=CPh2)(kappa2-MI)(CO)(PPh3)2]BF4. The hydride complexes [MH(kappa2-MI)(CO)(PPh3)2](M = Ru, Os) were obtained from the reaction of HMI and KOH with [RuHCl(CO)(PPh3)3] and [OsHCl(CO)(BTD)(PPh3)2], respectively. Reaction of [Ru(CH=CHC6H4CH3-4)(kappa2-MI)(CO)(PPh3)2] with excess HC triple bond CPh leads to isolation of the acetylide complex [Ru(C triple bond CPh)(kappa2-MI)(CO)(PPh3)2], which is also accessible by direct reaction of [Ru(C triple bond CPh)Cl(CO)(BTD)(PPh3)2] with 1-methyl-2-mercaptoimidazole and NaOMe. The thiocarbonyl complex [Ru(CPh = CHPh)Cl(CS)(PPh3)2] reacted with HMI and NaOMe without migration to yield [Ru(CPh= CHPh)(kappa2-MI)(CS)(PPh3)2], while treatment of [Ru(CH=CHPh)Cl(CO)2(PPh3)2] with HMI yielded the monodentate acyl product [Ru{eta(1)-C(=O)CH=CHPh}(kappa2-MI)(CO)(PPh3)2]. The single-crystal X-ray structures of five complexes bearing vinyl, aryl, acetylide and dienyl functionality are reported.     

Reactivity of diaminogermylenes with ruthenium carbonyl: Ru3Ge3 and RuGe2 derivatives

The nature of the products of the reactions of [Ru(3)(CO)(12)] with diaminogermylenes depends upon the volume and the cyclic or acyclic structure of the latter. Thus, the triruthenium cluster [Ru(3){μ-Ge(NCH(2)CMe(3))(2)C(6)H(4)}(3)(CO)(9)], which has a planar Ru(3)Ge(3) core and an overall C(3h) symmetry, has been prepared in quantitative yield by treating [Ru(3)(CO)(12)] with an excess of the cyclic 1,3-bis(neo-pentyl)-2-germabenzimidazol-2-ylidene in toluene at 100 °C, but under analogous reaction conditions, the acyclic and bulkier Ge(HMDS)(2) (HMDS = N(SiMe(3))(2)) quantitatively leads to the mononuclear ruthenium(0) derivative [Ru{Ge(HMDS)(2)}(2)(CO)(3)]. Mixtures of products have been obtained from the reactions of [Ru(3)(CO)(12)] with the cyclic and very bulky 1,3-bis(tert-butyl)-2-germaimidazol-2-ylidene under various reaction conditions. The Ru(3)Ge(3) and RuGe(2) products reported in this paper are the first ruthenium complexes containing diaminogermylene ligands.     

Photophysical properties of TiO(2) surfaces modified with dinuclear RuRu and RuOs polypyridyl complexes

The photophysical properties of nanoporous TiO(2) surfaces modified with two new Ru(II)-(bpt)-Ru(II) and Ru(II)-(bpt)-Os(II) polypyridyl complexes are reported. These dyads have been prepared by a two-step synthetic pathway. In the first step, [Ru(dcbpy)(2)Cl(2)], where dcbpy is 4,4'-dicarboxy-2,2-bipyridyl, was reacted with the bridging ligand 3,5-bis(pyridin-2-yl)-1,2,4-triazole (Hbpt) to yield the mononuclear precursor Na(3)[Ru(dcbpy)(2)(bpt)].3H(2)O. Subsequent reaction of this compound with either [Ru(bpy)(2)Cl(2)] or [Os(bpy)(2)Cl(2)] yields the Ru(II)-Ru(II) and Ru(II)-Os(II) dyads. Electrochemical data, together with time-resolved transient absorption spectroscopy and the investigation of the incident-photon-to-current-efficiency (IPCE), have been used to obtain a detailed picture of the photoinduced charge injection properties of these dyads. These measurements indicate that for the heterosupramolecular triad based on Ru(II)-(bpt)-Ru(II), the final product species obtained upon charge injection is TiO(2)(e)-Ru(II)Ru(III). For the mixed metal Ru(II)-(bpt)-Os(II) dyad, both metal centers inject efficiently into the semiconductor surface and as a result TiO(2)(e)-Ru(II)Os(III) is obtained as a single charge-separated product.     

Electronic structures of ruthenium and osmium complexes of 9,10-phenanthrenequinone

The reaction of 9,10-phenanthrenequinone (PQ) with [M(II)(H)(CO)(X)(PPh(3))(3)] in boiling toluene leads to the homolytic cleavage of the M(II)-H bond, affording the paramagnetic trans-[M(PQ)(PPh(3))(2)(CO)X] (M = Ru, X = Cl, 1; M = Os, X = Br, 3) and cis-[M(PQ)(PPh(3))(2)(CO)X] (M = Ru, X = Cl, 2; M = Os, X = Br, 4) complexes. Single-crystal X-ray structure determinations of 1, 2·toluene, and 4·CH(2)Cl(2), EPR spectra, and density functional theory (DFT) calculations have substantiated that 1-4 are 9,10-phenanthrenesemiquinone radical (PQ(?-)) complexes of ruthenium(II) and osmium(II) and are defined as trans-[Ru(II)(PQ(?-))(PPh(3))(2)(CO)Cl] (1), cis-[Ru(II)(PQ(?-))(PPh(3))(2)(CO)Cl] (2), trans-[Os(II)(PQ(?-))(PPh(3))(2)(CO) Br] (3), and cis-[Os(II)(PQ(?-))(PPh(3))(2)(CO)Br] (4). Two comparatively longer C-O [average lengths: 1, 1.291(3) ?; 2·toluene, 1.281(5) ?; 4·CH(2)Cl(2), 1.300(8) ?] and shorter C-C lengths [1, 1.418(5) ?; 2·toluene, 1.439(6) ?; 4·CH(2)Cl(2), 1.434(9) ?] of the OO chelates are consistent with the presence of a reduced PQ(?-) ligand in 1-4. A minor contribution of the alternate resonance form, trans- or cis-[M(I)(PQ)(PPh(3))(2)(CO)X], of 1-4 has been predicted by the anisotropic X- and Q-band electron paramagnetic resonance spectra of the frozen glasses of the complexes at 25 K and unrestricted DFT calculations on 1, trans-[Ru(PQ)(PMe(3))(2)(CO)Cl] (5), cis-[Ru(PQ)(PMe(3))(2)(CO)Cl] (6), and cis-[Os(PQ)(PMe(3))(2)(CO)Br] (7). However, no thermodynamic equilibria between [M(II)(PQ(?-))(PPh(3))(2)(CO)X] and [M(I)(PQ)(PPh(3))(2)(CO)X] tautomers have been detected. 1-4 undergo one-electron oxidation at -0.06, -0.05, 0.03, and -0.03 V versus a ferrocenium/ferrocene, Fc(+)/Fc, couple because of the formation of PQ complexes as trans-[Ru(II)(PQ)(PPh(3))(2)(CO)Cl](+) (1(+)), cis-[Ru(II)(PQ)(PPh(3))(2)(CO)Cl](+) (2(+)), trans-[Os(II)(PQ)(PPh(3))(2)(CO)Br](+) (3(+)), and cis-[Os(II)(PQ)(PPh(3))(2)(CO)Br](+) (4(+)). The trans isomers 1 and 3 also undergo one-electron reduction at -1.11 and -0.96 V, forming PQ(2-) complexes trans-[Ru(II)(PQ(2-))(PPh(3))(2)(CO)Cl](-) (1(-)) and trans-[Os(II)(PQ(2-))(PPh(3))(2)(CO)Br](-) (3(-)). Oxidation of 1 by I(2) affords diamagnetic 1(+)I(3)(-) in low yields. Bond parameters of 1(+)I(3)(-) [C-O, 1.256(3) and 1.258(3) ?; C-C, 1.482(3) ?] are consistent with ligand oxidation, yielding a coordinated PQ ligand. Origins of UV-vis/near-IR absorption features of 1-4 and the electrogenerated species have been investigated by spectroelectrochemical measurements and time-dependent DFT calculations on 5, 6, 5(+), and 5(-).     

Molecular wheels of ruthenium and osmium with bridging chalcogenolate ligands: edge-shared-octahedron structures and metal-ion binding

Inventing new wheels: reaction of [M(3)(CO)(12) ] (M=Ru, Os) with 4-RC(6)H(4)SH afforded [{M(S-4-RC(6)H(4))(2)(CO)(2)}(8)] (R=H; I) or [{M(S-4-RC(6)H(4))(2)(CO)(2)}(6)] (R=Me, iPr; II; see scheme), all of which have been structurally characterized. The octamers I are unique metal molecular wheels featuring skew-edge-shared octahedra with a central planar M(8) octagon. [{Ru(S-4-iPrC(6)H(4))(2)(CO)(2)}(6)] selectively binds a Cu(+) or Ag(+) ion to form [M'{Ru(S(4-iPr-C(6)H(4)))(2)(CO)(2)}(6)](+) (III).