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1.
《Inorganica chimica acta》1986,116(1):15-19
The crystal structure of the dimeric Ag maleonitriledithiolate complex, Ag2[S2C2(CN)2] [P(C6- H5)3]4 (1), has been performed. Complex 1 crystallizes in the space group P21/c with a = 12.2898(77), b = 23.8325(91), c = 23.1790(118) Å, β = 101.315(43)° and Z = 4. Refinement using 3253 reflections with Fo2>3σ(Fo2) yielded R = 0.0662, Rw= 0.0669. The most interesting aspect of the structure is the strong bridging interaction of the chelating maleonitriledithiolate ligand with the second Ag center, where a Ag-S distance of 2.478 Å is observed. The residual bonding capability of the sulfur atoms in the chelating anion [Ag(S2C2(CN)2)(PPh3)2]− for [Ag(PPh3)2]+ is demonstrated. 相似文献
2.
Yurii Simonov Paulina Bourosh Nicolae Gerbeleu Maria Gdaniec 《Inorganica chimica acta》2006,359(2):721-725
Two complexes of Au(III) with dimethylglyoxime of compositions [AuIII(HDMG)2][AuIIICl4] (1) and [AuIII(HDMG)2][AuICl2] (2) were synthesized and characterized by X-ray structural analysis. It was shown that in [AuIII(HDMG)2]+ cation Au(III) has a square-planar environment, and the oxygen atoms of oxime groups are joined by intramolecular H-bond. The secondary Au?Au and Au?Cl interactions in the crystal are discussed. 相似文献
3.
Shu Qin Liu Takayoshi Kuroda-Sowa Yusaku Suenaga Megumu Munakata 《Inorganica chimica acta》2005,358(4):919-926
Coordination polymers of [2.2]paracyclophane (pcp) with in situ silver(I) perfluoro-dicarboxylates characterized by single crystal X-ray analysis are described. Structures are found to strongly depend on the dicarboxylate spacer (n). With disilver(I) tetrafluorosuccinate ((CF2)n(COOAg)2, n = 2), 3D network with composition of [Ag4(pcp)(C2F4(CO2)2)2] (1) forms in which silver salts afford infinite double chains and pcp act as linkages between chains. Changing the silver salt to disilver hexafluoroglutarate ((CF2)n(COOAg)2, n = 3) produces 3D pillared-layer structure of composition of [Ag4(pcp)(C3F6(CO2)2)2] · THF (2) (THF = tetrahydrofuran), in which silver salts form 2D sheets and pcp act as pillars between the sheets. With silver octafluoroadipate (HO2C(CF2)nCO2Ag, n = 4), 2-fold interpenetrated diamond structure, [Ag2(pcp)2(HO2CC4F8CO2)2]2 · 2toluene (3), is obtained in which silver-anion chains and silver-pcp chains are connected with each other in the perpendicular manner. The three complexes represent unprecedented metal-organic networks of silver(I) multicarboxylates and polycyclic aromatic compounds. Additionally, the effects of the dicarboxylate conformations as well as the solvents on the resulting structures were discussed. 相似文献
4.
Fabiola Estudiante-Negrete Simón Hernández-Ortega David Morales-Morales 《Inorganica chimica acta》2007,360(5):1651-1660
The organometallic tin(IV) complexes [SnPh2(SRF)2] SRF = −SC6F4-4-H (1), −SC6F5 (2), were synthesized and their reactivity with [MCl2(PPh3)2] M = Ni, Pd and Pt explored. Thus, transmetallation products were obtained affording polymeric [Ni(SRF)(μ-SRF)]n, monomeric cis-[Pt(PPh3)2(SC6F4-4-H)2] (3) and cis-[Pt(PPh3)2(SC6F5)2] (4) and dimeric species [Pd(PPh3)(SC6F4-4-H)(μ-SC6F4-4-H)]2 (5) and [Pd(PPh3)(SC6F5)(μ-SC6F5)]2 (6) for Ni, Pt and Pd, respectively. The crystal structures of complexes 1, 2, 3, 4 and 6 were determined. 相似文献
5.
《Inorganica chimica acta》2006,359(15):4723-4729
Copper(I) and silver(I) complexes of formulae [Cu(NCCH3)4]+[A]− ([A]− = [B(C6F5)4]− (1), {B[C6H3(CF3)2]4}− (2), [(C6F5)3B–C3H3N2–B(C6F5)3]− (3), and [Ag(NCCH3)4]+[B(C6F5)4]− (4) are examined with particular emphasis on the strength of their M–N bond and its influence on the catalytic performance of these complexes in cyclopropanation and aziridination. To examine the strength of the M–N interactions, vibrational spectra of the related hydrogenated and deuterated species [Cu(NCCH3)4]+, [Cu(NCCD3)4]+, [Ag(NCCH3)4]+, and [Ag(NCCD3)4]+ are also determined. It is found that the metal–nitrile bond strength is an important factor for the catalytic activity of the respective complexes. 相似文献
6.
Electrospray ionisation mass spectrometry (ESI-MS) has been used as an analytical tool in a wide-ranging scoping study of the alkylation and arylation reactions of [Pt2(μ-S)2(PPh3)4]. From these experiments, the factors that influence the formation of different product species - formed by mono- or di-alkylation - are determined. If the alkylating agent is an alkyl chloride or sulfate, monoalkylation followed by dialkylation of the two sulfido groups occurs, dependent on the alkylating power of the reagent used. For example, n-butyl chloride gives solely [Pt2(μ-S)(μ-SBu)(PPh3)4]+ while dimethyl sulfate gives [Pt2(μ-SMe)2(PPh3)4]2+. This species, previously unisolated is stable in the absence of good nucleophiles, but the addition of potassium iodide results in rapid conversion to [Pt2(μ-SMe)2(PPh3)3I]+. This iodo complex is also observed from the reaction of [Pt2(μ-S)2(PPh3)4] with excess MeI, after the initial formation of mono- and di-methylated species. In these reactions, the iodide presumably displaces a phosphine ligand, which is then quaternised by excess alkylating agent. Changing the alkylating agent to a longer chain alkyl iodide or methyl bromide decreases the rate of alkylation of the sulfide in the initially formed [Pt2(μ-S)(μ-SR)(PPh3)4]+. Mixed-thiolate species of the type [Pt2(μ-SMe)(μ-SR)(PPh3)4]2+ are easily generated by reaction of [Pt2(μ-S)(μ-SR)(PPh3)4]+ with excess Me2SO4 and is also dependent on the avoidance of nucleophiles. Reactions towards α,ω-dialkylating agents are surveyed; the chain length is found to have a dramatic effect on the rate of the second intramolecular cyclisation process, illustrated by a competitive reactivity study involving a mixture of Br(CH2)4Br and Br(CH2)5Br; on completion of the reaction the former gives [Pt2{μ-S(CH2)4S}(PPh3)4]2+ while the latter predominantly gives monoalkylated[Pt2(μ-S){μ-S(CH2)5Br}(PPh3)4]+. The reactivity of o- and p-dihaloxylenes has been explored, with the reaction with p-BrCH2C6H4CH2Br giving the bridged species [(PPh3)4Pt2(μ-S)(μ-SCH2C6H4CH2S)(μ-S)Pt2(PPh3)4]2+. Arylation reactions of [Pt2(μ-S)2(PPh3)4] with halobenzenes and 2-bromoheterocyclic compounds (pyridine, thiophene) are also described. 相似文献
7.
The reactions of [Pt2(μ-S)2(PPh3)4] with α,ω-dibromoalkanes Br(CH2)nBr (n = 4, 5, 6, 8, 12) gave mono-alkylated [Pt2(μ-S){μ-S(CH2)nBr}(PPh3)4]+ and/or di-alkylated [Pt2(μ-S(CH2)nS}(PPh3)4]2+ products, depending on the alkyl chain length and the reaction conditions. With longer chains (n = 8, 12), intramolecular di-alkylation does not proceed in refluxing methanol, with the mono-alkylated products [Pt2(μ-S){μ-S(CH2)nBr}(PPh3)4]+ being the dominant products when excess alkylating agent is used. The bridged complex [{Pt2(μ-S)2(PPh3)4}2{μ-(CH2)12}]2+ was accessible from the reaction of [Pt2(μ-S)2(PPh3)4] with 0.5 mol equivalents of Br(CH2)12Br. [Pt2(μ-S){μ-S(CH2)4Br}(PPh3)4]+ can be cleanly isolated as its BPh4− salt, but undergoes facile intramolecular di-alkylation at −18 °C, giving the known species [Pt2(μ-S(CH2)4S}(PPh3)4]2+. The reaction of I(CH2)6I with [Pt2(μ-S)2(PPh3)4] similarly gives [Pt2(μ-S){μ-S(CH2)6I}(PPh3)4]+, which is fairly stable towards intramolecular di-alkylation once isolated. These reactions provide a facile route to ω-haloalkylthiolate complexes which are poorly defined in the literature. X-ray crystal structures of [Pt2(μ-S){μ-S(CH2)5Br}(PPh3)4]BPh4 and [Pt2(μ-S(CH2)5S}(PPh3)4](BPh4)2 are reported, together with a study of these complexes by electrospray ionisation mass spectrometry. All complexes fragment by dissociation of PPh3 ligands, and the bromoalkylthiolate complexes show additional fragment ions [Pt2(μ-S){μ-S(CH2)n−2CHCH2}(PPh3)m]+ (m = 2 or 3; m ≠ 4), most significant for n = 4, formed by elimination of HBr. 相似文献
8.
The reactivity of the metalloligand [Pt2(μ-S)2(PPh3)4] towards a variety of indium(III) substrates has been explored. Reaction with excess In(NO3)3 and halide (KBr or NaI) gave the four-coordinate adducts [Pt2(μ-S)2(PPh3)4InX2]+[InX4]− (X = Br, I). An X-ray structure determination on the iodo complex revealed a slightly distorted tetrahedral coordination geometry at indium. In contrast, reaction of [Pt2(μ-S)2(PPh3)4] with indium(III) chloride was more complex; the ion [Pt2(μ-S)2(PPh3)4InCl2]+ was initially observed in solution (using ESI mass spectrometry), and isolated as its BPh4− salt. Analysis of [Pt2(μ-S)2(PPh3)4InCl2]+[BPh4]− by ESI MS showed the parent cation when analysed in MeCN solution. However in solutions containing methanol, partial solvolysis occurred to give the di-indium species [{Pt2(μ-S)2(PPh3)4InCl(OMe)}2]2+ (proposed to contain an In2(μ-OMe)2 unit with five-coordinate indium) and its fragment ion [Pt2(μ-S)2(PPh3)4InCl(OMe)]+. Reaction of [Pt2(μ-S)2(PPh3)4] with InCl3·3H2O, 8-hydroxyquinoline (HQ) and trimethylamine in methanol gave the adduct [Pt2(μ-S)2(PPh3)4InQ2]+, isolated as its PF6− salt. The same cationic complex is formed when [Pt2(μ-S)2(PPh3)4] is reacted with InQ3 in methanol, but in this case the product is contaminated with the mononuclear complex [(Ph3P)2PtQ]+ formed by disintegration of the trinuclear complex [Pt2(μ-S)2(PPh3)4InQ2]+ with byproduct Q−. [(Ph3P)2PtQ]+BPh4− was independently prepared from cis-[PtCl2(PPh3)2] and HQ/Me3N, and is the first example of a platinum 8-hydroxyquinolinate complex containing phosphine ligands. 相似文献
9.
Reaction of the metalloligand [Pt2(μ-S)2(PPh3)4] with the N-heterocyclic carbene (NHC) complexes IPrAuCl, IMesAuCl and IMesAgCl in methanol gave the first examples of metal adducts of [Pt2(μ-S)2(PPh3)4] that contain NHC ligands, namely [Pt2(μ-S)2(PPh3)4AuL]+ (L = IPr, IMes) and [Pt2(μ-S)2(PPh3)4AgIMes]+. The complexes were isolated as hexafluorophosphate salts. Reaction of [Pt2(μ-S)2(PPh3)4] with excess IPrAuCl in refluxing methanol yielded only the mono-adduct, in contrast to the behaviour with the gold(I) phosphine complex Ph3PAuCl, which undergoes double addition giving [Pt2(μ-SAuPPh3)2(PPh3)4]2+. The X-ray structure of [Pt2(μ-S)2(PPh3)4AuIPr]PF6 was determined and reveals that the ‘free’ sulfide is substantially sterically protected by the IPr ligand, accounting for the low reactivity towards addition of a second AgIPr+ moiety. 相似文献
10.
Lourdes Cabrera 《Inorganica chimica acta》2006,359(9):3066-3071
Trityl borate salts [4-RPyCPh3][B(C6F5)4] (R = H 1, tBu 2, Et 3, NMe24) and [R3PCPh3][B(C6F5)4] (R = Me 5, nBu 6, Ph[1] 7, p-MeC6H48) are readily prepared via equimolar reaction of the appropriate pyridine or phosphine and trityl borate [CPh3][B(C6F5)4]. The analogous reactions of PiPr3 affords the product [(p-iPr3P-C6H4)Ph2CH][B(C6F5)4] (9) while the corresponding reactions of Cy3P and tBu3P gave the cyclohexadienyl derivatives [(p-R3PC6H5)CPh2][B(C6F5)4] (R = Cy 10, tBu 11). X-ray structures of 5 and 9 are reported. 相似文献
11.
The preparation and structures of the bismuth thiolato anions [Bi2(SC6F5)6(μ-SC6F5)]− and [Bi2(SC6F5)6(μ-SC6F5)2]2− and the halothiolato anions [Bi2(SC6F5)6(μ-Br)]−, [Bi2(SC6F5)6(μ-Cl)2]2− and [Bi3(SC6F5)9(μ-Br)2]2− are described. All compounds have been isolated from reactions between Bi(SC6F5)3 and ammonium or phosphonium halides. The basic structural units in the dinuclear species are of two types namely [Bi2(SR)6(μ-X)]− and [Bi2(SR)6(μ-X)2]2−, where X=thiolate or halide. In the former case the single bridging groups occupy an axial site within the disphenoidal (equatorially vacant, trigonal bipyramidal) geometry around the bismuth centres whereas in the latter the two bridging groups occupy cis basal sites in square based pyramidal bismuth environments. The trinuclear anion [Bi3(SC6F5)9(μ-Br)2]2− has features in common with the basic [Bi2(SC6F5)6(μ-Br)]− unit. 相似文献
12.
The reactivity of [Pt2(μ-S)2(PPh3)4] towards a range of nickel(II) complexes has been probed using electrospray ionisation mass spectrometry coupled with synthesis and characterisation in selected systems. Reaction of [Pt2(μ-S)2(PPh3)4] with [Ni(NCS)2(PPh3)2] gives [Pt2(μ-S)2(PPh3)4Ni(NCS)(PPh3)]+, isolated as its BPh4 − salt; the same product is obtained in the reaction of [Pt2(μ-S)2(PPh3)4] with [NiBr2(PPh3)2] and KNCS. An X-ray structure determination reveals the expected sulfide-bridged structure, with an N-bonded thiocyanate ligand and a square-planar coordination geometry about nickel. A range of nickel(II) complexes NiL2, containing β-diketonate, 8-hydroxyquinolinate, or salicylaldehyde oximate ligands react similarly, giving [Pt2(μ-S)2(PPh3)4NiL]+ cations. 相似文献
13.
Routes to the synthesis of the mixed sulfide-phenylthiolate complex [Pt2(μ-S)(μ-SPh)(PPh3)4]+ have been explored; reaction of [Pt2(μ-S)2(PPh3)4] with excess Ph2IBr proceeds readily to selectively produce this complex, which was structurally characterised as its PF6− salt. Reactions of [Pt2(μ-S)2(PPh3)4] with other potent arylating reagents (1-chloro-2,4-dinitrobenzene and 1,5-difluoro-2,4-dinitrobenzene) also produce the corresponding nitroaryl-thiolate complexes [Pt2(μ-S){μ-SC6H2(NO2)2X}(PPh3)4]+ (X = H, F). The complex [Pt2(μ-S)(μ-SPh)(PPh3)4]+ reacts with Me2SO4 to produce the mixed alkyl/aryl bis-thiolate complex [Pt2(μ-SMe)(μ-SPh)(PPh3)4]2+, but corresponding reactions with the nitroaryl-thiolate complexes are plagued by elimination of the nitroaryl group and formation of [Pt2(μ-SMe)2(PPh3)4]2+. [Pt2(μ-S)(μ-SPh)(PPh3)4]+ also reacts with Ph3PAuCl to give [Pt2(μ-SAuPPh3)(μ-SPh)(PPh3)4]2+. 相似文献
14.
Phosphonium zwitterions of a known type were obtained in high yield via a 1:1 reaction of p-benzoquinone or methoxy-p-benzoquinone with the tertiary phosphines R3P [R = (CH2)3OH, Ph, Et, Me] and Ph2MeP, in acetone or benzene at room temperature. In all cases, attack of the P-atom occurs at a C-atom rather than at an O-atom. The products were characterized to various degrees by elemental analysis, 31P{1H}, 1H and 13C NMR spectroscopies, and mass spectrometry, and two of the zwitterions, the new [HO(CH2)3]3P+C6H2(O−)(OH)(MeO) and the known Ph3P+C6H3(O−)(OH), were structurally characterized by X-ray analysis. The PEt3 reaction also produces small amounts of the ‘dimeric’, μ-oxo co-product Et3P+C6H2(O−)(OH)-O-C6H3(O−)P+Et3 that is tentatively characterized by 1D- and 2D-NMR data. 2,5-Di-tert-butyl- and 2,3,5,6-tetramethyl-p-benzoquinone do not react with [HO(CH2)3]3P under the conditions noted above. Heating D2O solutions of the water-soluble zwitterions R3P+C6H3(O−)(OH) [R = (CH2)3OH, Et] at 90 °C for 72 h leads to complete H/D exchange of the H-atom in the position ortho to the phosphonium center. 相似文献
15.
Liqing Ma 《Inorganica chimica acta》2005,358(12):3478-3482
The reaction of [Pd(OAc)2(py)2] with [Li((OEt2)2.5)][B(C6F5)4] was conducted with intent to generate the cationic palladium complex [Pd(OAc)(py)3][B(C6F5)4], (2, py = pyridine). A single crystal structure of this material, however, reveals a 1-D polymer structure formed by the self-assembly of alternating dicationic ([Pd(py)4]2+) and neutral ([Pd(OAc)2(py)2]) palladium units bridged by acetato linkages to give [Pd(py)4][Pd(OAc)2(py)2][B(C6F5)4]2 (3). These two palladium sites are produced by disproportionation of the pyridine ligands in [Pd(OAc)(py)3][B(C6F5)4]. Proton NMR studies confirm the existence of a solvent dependent equilibrium between [Pd(py)4]2+, [Pd(OAc)2(py)2] and [Pd(OAc)(py)3]+. 相似文献
16.
《Inorganica chimica acta》2004,357(8):2331-2338
The di-μ-hydroxo complexes [NBu4]2[{(C6F5)2M(μ-OH)}2] (M=Pd, Pt) react with PhNCS in alcohol ROH solution to yield the N,S-chelating thiocarbamate metal complexes [NBu4][(C6F5)2M{η2-SC(OR)NPh}] (R=Me, Et or Prn). [NBu4]2[{(C6F5)2Pd(μ-OH)}2] also reacts with PhNCS in the presence of dialkylamines R2NH to yield the N,S-chelating thioureate (1−) palladium complexes [NBu4][(C6F5)2Pd{η2-SC(NR2)NPh}] (R=Me or Et). [NBu4][(C6F5)2M{η2-SC(X)NPh}] (M=Pd or Pt; X=OMe or NR2) reacts with [(C6F5)Pd(bpzm)(acetone)]ClO4 to yield the dinuclear complexes [(C6F5)2M{(μ2,η2-{SC(X)NPh}Pd(C6F5)(bpzm)] (M=Pd or Pt, X=OMe or NR2; bpzm=bis(3,5-dimethylpyrazol-1-yl)methane). The single-crystal structures of [NBu4][(C6F5)2Pd{η2-SC(OMe)NPh}] and [(C6F5)2Pd{μ2,η2-SC(NMe2)NPh}Pd(C6F5)(bpzm)] have been established by X-ray diffraction. 相似文献
17.
P.A. Abramov M.N. Sokolov E.V. Peresypkina N.K. Moroz R. Hernandez-Molina M.C. Arévalo 《Inorganica chimica acta》2011,375(1):314-319
New cluster complex [Mo3SeO3(acac)3(py)3]+ was obtained by ligand substitution in the aqua complex [Mo3SeO3(H2O)9]4+. Crystal structure was determined for [Mo3SeO3(acac)3(py)3]PF6·C6H5CH3. The complex was characterized by 77Se NMR, electrospray mass-spectrometry, and cyclic voltammetry. DFT calculations were used to confirm the assignment of chemical shift and to study Mo-Mo bonding in the cluster core. 相似文献
18.
Systematic survey on the reactions of silver nitrate with H3Ssal ligand (H3Ssal = 5-sulfo-salicylic acid) accompanying with different alkali metal ions under alkali conditions leads to two novel luminescent alkali-silver heterometallic sulfonates, [KAg(HSsal)(H2O)3]n (1) with a 3-D structure constructed by [K2O10] binuclear units linking 1-D∞1[Ag2(HSsal)2] double chains, [NaAg(HSsal)(H2O)3]n (2) with a 3-D structure constructed by the [Ag2(HSsal)2] dimers connecting 1-D∞1[NaO6] chains, and also reveals the coordination strength of the alkali metal cations and Ag+ towards the sulfonate groups with K+ > Na+ > Ag+ > Li+ order. The two compounds show intense blue emissions in both solid state and water solution. 相似文献
19.
Val Phillips Tania Lasanta Jeffrey W. Bacon Arnold L. Rheingold 《Inorganica chimica acta》2010,364(1):195-204
A comparative study of metallophilic interactions of [Pt(tpy)X]+ cations (tpy = 2,2′:6′,2″-terpyridine) in the presence of two different types of anions, (i) []− anions that form double salts and (ii) simple p-block anions, is reported. Single-crystal X-ray diffraction data, solution-state 195Pt NMR spectra, and variable temperature solid-state luminescence spectra are reported. Three [Pt(tpy)Cl]Y derivatives (Y = SbF6, 1, SbF6·CH3CN, 4, PF6, 2) and the [Pt(tpy)Br]PF6 analog, 3, as well as two new double salts [Pt(tpy)CN][Au(CN)2], 5, and [Pt(tpy)CN]2[Au(C6F5)2](PF6), 6, have been synthesized and characterized. Structural analysis shows consistent patterns in Pt···Pt interactions that vary slightly depending on the coordinating halogen or pseudo-halogen X, counter anion Y, and lattice solvent. Metallophilic interactions are seen between [Pt(tpy)X]+ cations with all types of X ligands, but only with π-accepting X′ ligands from []− anions are Pt?Au metallophilic interactions seen to be favored over Pt?Pt interactions. The [Au(CN)2]− anion consistently forms Pt···Au metallophilic contacts, unlike [Au(C6F5)2]−. The 195Pt NMR chemical shifts are ∼−2750 ppm for π-donor ligands and near −3120 ppm for π-acceptor ligands in [Pt(tpy)X]PF6 compounds. Luminescence data show an unusual blue shift in [Pt(tpy)CCPh][Au(C6F5)2] versus [Pt(tpy)CCPh]PF6 ascribed to an intermolecular charge transfer. 相似文献
20.
Konstantinos D. Demadis Edward M. Kober Peter S. White 《Inorganica chimica acta》2007,360(3):1143-1153
Structural changes between [OsIIL3]2+ and [OsIIIL3]3+ (L: 2,2′-bipyridine; 1,10-phenanthroline) and molecular and electronic structures of the OsIII complexes [OsIII(bpy)3]3+ and [OsIII(phen)3]3+ are discussed in this paper. Mid-infrared spectra in the ν(bpy) and ν(phen) ring stretching region for [OsII(bpy)3](PF6)2, [OsIII(bpy)3](PF6)3, [OsII(phen)3](PF6)2, and [OsIII(phen)3](PF6)3 are compared, as are X-ray crystal structures. Absorption spectra in the UV region for [OsIII(bpy)3](PF6)3 and [OsIII(phen)3](PF6)3 are dominated by very intense absorptions (ε = 40 000-50 000 M−1 cm−1) due to bpy and phen intra-ligand π → π∗ transitions. In the visible region, relatively narrow bands with vibronic progressions of ∼1500 cm−1 appear, and have been assigned to bpy or phen-based, spin-orbit coupling enhanced, 1π → 3π∗ electronic transitions. Also present in the visible region are ligand-to-metal charge transfer bands (LMCT) arising from π(bpy) → t2g(OsIII) or π(phen) → t2g(OsIII) transitions. In the near infrared, two broad absorption features appear for oxidized forms [OsIII(bpy)3](PF6)3 and [OsIII(phen)3](PF6)3 arising from dπ-dπ interconfigurational bands characteristic of dπ5OsIII. They are observed at 4580 and 5090 cm−1 for [OsIII(bpy)3](PF6)3 and at 4400 and 4990 cm−1 for [OsIII(phen)3](PF6)3. The bpy and phen infrared vibrational bands shift to higher energy upon oxidation of Os(II) to Os(III). In the cation structure in [OsIII(bpy)3](PF6)3, the OsIII atom resides at a distorted octahedral site, as judged by ∠N-Os-N, which varies from 78.78(22)° to 96.61(22)°. Os-N bond lengths are also in general longer for [OsIII(bpy)3](PF6)3 compared to [OsII(bpy)3](PF6)2 (0.010 Å), and for [OsIII(phen)3](PF6)3 compared to [OsII(phen)3](PF6)2 (0.014 Å). Structural changes in the ligands between oxidation states are discussed as originating from a combination of dπ(OsII) → π∗ (bpy or phen) backbonding and charge redistribution on the ligands as calculated by natural population analysis. 相似文献