Allyldialkyl complexes of ruthenium(IV): Preparation and reductive CC bond formation followed by CH bond activation

New η³-allyldimethyl complexes Ru(η⁵-C₅R₅)(η³-C₃H₅)(CH₃)₂, where R = H or CH₃, are prepared from Ru(η⁵-C₅R₅)(η³-C₃H₅)Br₂ by alkylation with trimethyl-aluminium. The Ru^IV dimethyl complex is thermally converted to the Ru^II 1-methylallyl compound, Ru(η⁵-C₅R₅)(η³-CH₂CHCHCH₃)L, where L = CO or t-C₄H₉NC, with evolution of methane. Kinetic and deuteration studies on the reductive process are also discussed.     

Photochemical reactions of allyl and crotyl halides with cyclopentadienyl-chromium, -molybdenum and -tungsten complexes

[MoCl(CO)₃(η⁵-C₅H₅)] on photolysis with allyl or crotyl halides C₅H₄RX gives Mo^IV complexes [MoX₂(CO)(η³-C₃H₄R)(η⁵-C₅H₅)] (R = H, X = Cl, Br, I; R = Me, X = Cl, Br). [WCl(CO)₃(η⁵-C₅H₅)] under similar conditions gives trihalides [WX₃(CO)₂(η⁵-C₅H₅)] (X = Cl, Br) on reaction with C₃H₅Cl and C₃H₅Br while [WCl(CO)₃(η⁵-C₅H₄SiMe₃)] and [CrI(CO)₃(η⁵-C₅H₅)] react with allyl chloride to give [WCl₃(CO)₂(η⁵-C₅H₄SiMe₃)] and [CrCl₂(η⁵-C₅H₅)] respectively.     

TRITHIA-DIPHOSPHABIYCLO[2.2.1]HEPTANE

Abstract

3,6-Dialkyl-2,5-Dithioxo-1,4,2λ⁵,5λ⁵-dithiadiphosphorinan-2,5-disulfides (1) react with PSCI₃, to give 3,6-Dialkyl(diaryl)-1,4-dithioxo-2,5,7-trithia-lλ⁵,4λ⁵ diphosphabicyclo[2.2.1]heptanes (2). The reaction mechanism of their formation. and the stereochemistry are discussed. By reduction of 2 with (n-C₄H₉)₃P or (C₆H₅),P 3,6-Dialkyl-2,5,7-trithia-1λ³,4λ³-diphosphabicyclo[2.2.1]heptanes (3) are formed. 2c reacts with one mole of (C₆H₅)₃P to give 3,6-Diethyl-l-thioxo-2,5,7-trithia-lλ⁵,4λ³- diphosphabicyclo(2.2.1]heptane, 4c.

3,6-Dialkyl-2,5-dithioxo-1.4,2λ⁵,5λ⁵-dithiadiphosphorinan-2,5-disulfide (I) reagieren mit PSCI₃ zu 3,6-Dialkyl(diaryl)-1,4-dithioxo-2,5,7-trithia-lλ⁵,4λ⁵-diphosphabicyclo[2.2.l]heptanen (2). Der Reaktionsmechanismus ihrer Bildung und ihre Stereochemie werden diskutiert. Die Reduktion von 2 mit (n-C₄H₉)₃,P oder (C₆H₅)₃P führt zu 3,6-Dialkyl-2,5,7-trithia-1λ³,4λ³-diphosphabicyclo[2.2.1] heptanen(3). 2c reagiert mit einer äquimolaren Menge (C₆H₅)₃,P zu 3,6-Diethyl-l-thioxo-2,5,7-trithia-lλ⁵,4λ³- diphosphabicyclo[2.2.1]heptan, 4c.     

Luminescence Tuning of Upconversion Nanocrystals

Upconversion luminescence tuning of β‐NaYF₄ nanorods under 980 nm excitation has successfully been achieved by tridoping with Ln³⁺ ions with different electronic structures. The effects of Ce³⁺ ions on NaYF₄:Yb³⁺/Ho³⁺ as well as Gd³⁺ ions on NaYF₄:Yb³⁺/Tm³⁺(Er³⁺) have been studied in detail. By tridoping with Ce³⁺ ions, not only were unusual ⁵G₅→⁵I₇ and ⁵F₂/³K₈→⁵I₈ transitions from Ho³⁺ ions and 5d→4f transitions from Ce³⁺ ions observed in NaYF₄:Yb³⁺/Ho³⁺ nanorods, but also an increase in the intensity of ⁵F₅→⁵I₈ relative to ⁵S₂/⁵F₄→⁵I₈ with increasing Ce³⁺ concentration, which can be attributed to efficient energy transfers of ⁵I₆ (Ho)+²F_5/2 (Ce)→⁵I₇ (Ho)+²F_7/2 (Ce) and ⁵S₂/⁵F₄ (Ho)+²F_5/2 (Ce)→⁵F₅ (Ho)+²F_7/2 (Ce). Interestingly, with increasing pump power density, the luminescence of NaYF₄:Yb³⁺/Ho³⁺ nanorods is always dominated by the ⁵S₂/⁵F₄→⁵I₈ transition, whereas the luminescence of Ce³⁺‐tridoped NaYF₄:Yb³⁺/Ho³⁺ nanorods is dominated by the ⁵S₂/⁵F₄→⁵I₈ and ⁵G₅→⁵I₇ transitions in turn. These observations are discussed on the basis of a rate equation model. Furthermore, Gd³⁺‐tridoped NaYF₄:Yb³⁺/Tm³⁺(Er³⁺) nanorods can emit multicolor upconversion emissions spanning from the UV to the near‐infrared under 980 nm excitation. ⁶P_5/2→⁸S_7/2 (≈306 nm) and ⁶P_7/2→⁸S_7/2 (≈311 nm) transitions from Gd³⁺ ions were observed. In addition to the aforementioned luminescence properties, these Gd³⁺‐tridoped nanorods also exhibit paramagnetic behavior at room temperature and superparamagnetic behavior at 2 or 5 K.     

Übergangsmetall-Komplexe des 1,1,3,3-Tetrakis(dimethylamino)-1λ5,3λ5-diphosphets

Transition Metal Complexes of 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3λ⁵-Diphosphete 1,1,3,3-Tetrakis(dimethylamino)-1λ⁵,3aλ⁵-diphosphete, 1 , reacts with W(CO)₆ to yield the isomeric complexes {1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete}(pentacarbonyl)tungsten 4 and {1,1,3,3-tetrakis(dimethylamino)-1,4-dihydro-1λ⁵,3λ⁵-[1,3]diphosphetium}(pentacarbonyl)tungsten 5 . With Cr(CO)₆ the complex {1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete}(pentacarbonyl)chromium 6 is formed. From the reaction products of Fe₃(CO)₁₂ and Fe₂(CO)₉ with 1 the complex {1,1,3,3-tetrakis(dimethylamino)-1λ⁵,3λ⁵-diphosphete}(pentacarbonyl)iron 7 could be isolated. Properties, nmr, ir and mass spectra of the new compounds are reported. 6 and 7 were characterized by X-ray structure determinations.     

Nickelocene chemistry : II. New methylidyne trinickel cluster compounds

The new methylidene trinickel cluster complexes, [RCNi₃(η⁵-C₅H₅₃] (R  CMe₃ or SiMe₃) and [Me₃SiCNi₃(η⁵-C₅H₅)2(η⁵-C₅H₄CH₂SiMe₃)] have been isolated in low yield from reactions between nickelocene and the corresponding alkyllithium reagents, RCH₂Li. The compounds [RCNi₃(η⁵-C₅H₅)₃] (R  Ph, CMe₃ or SiMe₃) have also been obtained by treatment of the σ-alkylnickel complexes [(η⁵-C₅H₅)Ni(CH₂R)(PPh₃)] with n-BuLi in the presence of an excess of nickelocene, but under similar conditions [(η⁵-C₅H₅)Ni(CH₂C_1OH₇-2)-(PPh₃)] (where C_1OH₇-2  2-naphthyl) failed to give [2-C_1OH₇CNi₃(η⁵-C₅H₅)₃]. The attempted synthesis of [(η⁵-C₅H₅)Ni(CH₂CCH)(PPh₃)] from [(η⁵-C₅H₅)-NiBr(PPh₃)] and CHCCH₂MgBr gave only [(η⁵-C₅H₅)Ni(CCMe)(PPh₃)] by an unusual rearrangement reaction.     

Porphyrins. 18. Synthesis of octapropylporphyrin by the method of monopyrrole cyclotetramerization of 5-carboxy-2-methoxymethyl-3,4-dipropylpyrrole. Investigation of the thermolysis of meso-N-methylformaldimineocta-propylporphyrin

The synthesis of octapropylporphyrin on the basis of 5-carboxy-2-methoxymethyl-3,4-dipropylpyrrole was realized. It was demonstrated that in the thermolysis of meso-N-methylformaldimineoctapropylporphyrin, 3¹,5¹-cyclo-3¹-ethylidene- and 3¹,5¹-cyclo-3¹-ethyl-5¹-(N-methylimine) derivatives are also formed in addition to 3¹,5¹-cyclo-3¹-ethylhectaporphyrin.See [1] for Communication 17.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 922–927, 1984.     

Reaktionen von tricarbonyl-chrom-η6λ3-phosphorin-komplexen zu tricarbonyl-chrom-η6λ5-phosphorin-ylid-komplexen

The tricarbonylchromium η⁶π⁶ complexes of 2,4,6-triphenyl- and 2,4,6-tri-t-butyl-λ³-phosphorins 3a and 3b add nucleophiles regio- and stereo-specifically to the phosphorus atom in the exo-position giving the λ⁴-phosphorin anions which now add electrophiles in the endo position, giving η⁵π⁶-λ⁵-phosphorin ylide complexes 5a and 5b, respectively. The ¹H, ¹³C and ³¹P NMR spectra of 3a and 3b and especially 5a and 5b are discussed with respect to the stereoisomeric complexes 5a having two different exocylic substituents at the phosphorus atom, synthesized from e.g. 1-ethyl-1-methyl-2,4,6-triphenyl-λ⁵-phosphorin and Cr(CO)₆. The tricarbonylchromium-1,1,-dialkyl or alkyl-aryl-2,4,6-tri-t-butyl-λ⁵-phosphorin 5b can only be synthezised from tricarbonylchromium-2,4,6-tri-t-butyl-λ³-phosphorin by addition of nucleophiles and electrophiles since the corresponding λ⁵-phosphorin derivatives are not available. By removal of the tricarbonylchromium residue from the λ⁵-phosphorin-ylide complexes 5b, however, also 2,4,6-tri-t-butyl-λ⁵-phosphorins can be prepared.     

Synthesis and structures of the η5-C5H5Cl(CO)2W-η1,η5-(PPh2)C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)3 and MeSi[C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)2PPh3]3 complexes

The metallation of the η⁵-C₅H₅(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃ complex with BuⁿLi (THF, ?78 °C) followed by the treatment of the lithium derivative with Ph₂PCl afforded the η⁵-Ph₂PC₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃ complex. The reaction of the latter with η⁵-C₅H₅(CO)₃WCl in the presence of Me₃NO produced the trinuclear complex η⁵-C₅H₅Cl(CO)₂W-η¹,η⁵-(Ph₂P)C₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₃. The structure of the latter complex was established by IR, UV, and 1H and ³¹P NMR spectroscopy and X-ray diffraction. The reaction of MeSiCl₃ with three equivalents of LiC₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₂PPh₃ gave the hexanuclear complex MeSi[C₅H₄(CO)₂Fe-η¹,η⁵-C₅H₄Mn(CO)₂PPh₃]₃.     

Interactions of Eu3+(aq) 7F, 5D1 and 5D0 levels with nitrate and inner-sphere (EuNO2+3)* exciplex formation

Steady-state and transient photokinetic and spectroscopic measurements on aqueous Eu(NO₃)₃ show different affinities of ⁷F, ⁵D₁ and ⁵D₀ Eu³⁺_aq towards nitrate ion. This may be rationalised by differences in the inner- and outer-shell hydration structures between ⁵D_O, ⁵D₁ Eu³⁺(_aq) and ⁷F Eu³⁺_(aq). Nitrate penetration into the inner-shell of Eu³⁺_(aq), and inner-coordination (EuNO²⁺₃)^* exciplex formation, occur solely in the long-lived ⁵D_O level of Eu³⁺_(aq).     

Strukturdynamische organometall-komplexe: III. Synthese,struktur und bindungsverhältnisse der komplexe (η5-C5H5)Pd(η1-C5H5)PR3

The complexes (η₅-C₅H₅)Pd(η¹-C₅H₅)PR₃ which are prepared from [Cl(PR₃)-Pd]₂(μ-OCOCH₃)₂ and TlC₅H₅ are fluxional in solution. According to the ¹H and ¹³C NMR spectra at various temperatures, two dynamic processes occur. The process with the higher activation energy is a π/σ (η⁵/η¹) exchange of the two different cyclopentadienyl ligands, whereas the second one with the lower activation energy presumably is a metallotropic rearrangement (1,2-shift). The coalescence temperature for the η⁵/η¹ exchange depends on the size of the phosphine. The X-ray structural analysis of (C₅H₅)₂PdPPrⁱ₃ proves that it exists as a “frozen” η⁵ + η¹ structure in the crystal with the palladium approximately in a square-planar coordination. The η⁵-bonded cyclopentadienyl ring shows some unusual bonding patterns which are obviously electronic in nature. EHT-MO calculations for (η⁵-C₅H₅)PdCH₃(PH₃) indicate that in this model system alternating CC distances in the ring and a stronger bond of the metal to one of the five carbon atoms of the C₅H₅ ligand are to be expected. The calculations suggest that in similar complexes possessing a six-electron donor ligand like C₅H₅^? and a metal fragment which is isolobal to PdCH₃(PH₃)⁺, analogous distortions should be observed. Some reactions of the compounds (η⁵-C₅H₅)Pd(η¹-C₅H₅)PR₃ are described.     

Intense Upconversion Luminescence of CaSc2O4:Ho3+/Yb3+ from Large Absorption Cross Section and Energy‐Transfer Rate of Yb3+

Concentration‐optimized CaSc₂O₄:0.2 % Ho³⁺/10 % Yb³⁺ shows stronger upconversion luminescence (UCL) than a typical concentration‐optimized upconverting phosphor Y₂O₃:0.2 % Ho³⁺/10 % Yb³⁺ upon excitation with a 980 nm laser diode pump. The ⁵F₄+⁵S₂→⁵I₈ green UCL around 545 nm and ⁵F₅→⁵I₈ red UCL around 660 nm of Ho³⁺ are enhanced by factors of 2.6 and 1.6, respectively. On analyzing the emission spectra and decay curves of Yb³⁺: ²F_5/2→²F_7/2 and Ho³⁺: ⁵I₆→⁵I₈, respectively, in the two hosts, we reveal that Yb³⁺ in CaSc₂O₄ exhibits a larger absorption cross section at 980 nm and subsequent larger Yb³⁺: ²F_5/2→Ho³⁺: ⁵I₆ energy‐transfer coefficient (8.55×10^?17 cm³ s^?1) compared to that (4.63×10^?17 cm³ s^?1) in Y₂O₃, indicating that CaSc₂O₄:Ho³⁺/Yb³⁺ is an excellent oxide upconverting material for achieving intense UCL.     

Nickelocene chemistry : III. Reactions of Bromo(η5-cyclopentadienyl)triphenylphosphinenickel with phosphorus,arsenic and sulphur ylids

The phosphorus ylids Ph₃PCHR (R = Me, Et, Prⁿ, Prⁱ, Bu_n, Cl, and OMe), and the ylids Ph₃AsCH₂, Me₂SCH₂, and Me₂S(O)CH₂ react with [Ni(η⁵-C₅H₅)Br(PPh₃)] at room temperature to give the complexes [Ni(Ph₃PCHR)(η⁵-C₅H₅(PPh₃)] Br, [Ni(Ph₃AsCH₂)(η⁵-C₅H₅)(PPh₃)]Br, [Ni(Me₂SCH₂)(η⁵-C₅H₅)(PPh₃)]Br and [Ni{Me₂S(O)CH₂} (η⁵-C₅H₅)(PPh₃)]Br, respectively. These are readily converted into the corresponding hexafluorophosphate salts on reaction with ammonium hexafluorophosphate. Under more forcing conditions the stabilised ylid Ph₃PCHCOPh gives a product believed to be the complex [Ni(Ph₃PCHCOPh)₂(η⁵-C₅H₅)]Br, isolated and characterised as its PF₆^? salt.     

New neutral and cationic cyclopentadienylcobalt complexes

The treatment of the aquocation [Co(η³-2-MeC₃H₄)(η⁵-C₅H₅)(H₂O]⁺ with neutral and anionic ligands gives new cobalt complexes containing cations [Co(η³-2-MeC₃H₄)(η⁵-C₅H₅)L]ⁿ⁺, n = 0; L = CN, CH₃COO, CF₃COO and n = 1; L = P(p-MePh)₃, NCEt, NCPh, CNCy, dppm and [{Co(η³-2-MeC₃H₄)(η⁵-C₅H₅)}₂ (μ-L-L)]²⁺, L-L = bipy, dppm. The neutral cyano complex reacts with various electrophiles to give cationic isocyanide complexes containing the cation [Co(η³-2-MeC₃H₄)(η⁵-C₅H₅)(CNR)]⁺, which have been isolated in low yields. Chemical behaviour and structural implications of IR and ¹H and ¹³C NMR spectra are discussed.     

Transition metal nitrosyls as nitrosylation agents : II.Photo-nitrosylation of η5-C5H5V(CO)3L(L = CO,Pz3) by [Co(NO)2Br]2

η⁵-C₅H₅V(NO)₂CO is prepared in 40% yield by the photo-reaction between η⁵-C₅H₅V(CO)₄ and [Co(NO)₂Br]₂.η⁵-C₅H₅V(NO)₂CO reacts by an S_N1 mechanism with various phosphines PZ₃ to yield η⁵-C₅-H₅V(NO)₂PZ₃. The phosphine complexes are also obtained by photo-induced ligand interchange between η⁵-C₅H₅V(CO)₃PZ₃ and [Co(NO)₂Br]₂, or η⁵-C₅H₅V(CO)₄ and Co(NO)₂Br(PZ₃). In all cases, the main cobalt species formed is Co(NO)(CO)₃. While the one-bond vanadiumphosphorus coupling constants of most of the phosphine complexes are virtually the same (ca 410 Hz),the chemical shift values δ(⁵¹V) (?1328 to ?973 ppm rel. VOCl₃) decrease in the order PF₃ > CO > P(OR)₃ > P(alkyl)₃ > PPh₃ > PPh(NEt₂)₂, reflecting the decreasing π-acceptor ability of the ligands. δ(⁵¹V) also decreases in the series of alkylphosphines PR₃ (R = Me, Et, Prⁿ, Buⁱ, Prⁱ, BU^t) as the cone angle of PR₃increases.     

Stepwise TiCl,TiCH3, and TiC6H5 bond dissociation enthalpies in bis(pentamethylcyclopentadienyl)titanium complexes

Reaction-solution calorimetric studies involving the complexes Ti[η⁵-C₅(CH₃)₅]₂-(CH₃)₂, Ti[η⁵-C₅(CH₃)₅]₂(CH₃), Ti[η⁵-C₅(CH₃)₅]₂(C₆H₅), Ti[η⁵-C₅(CH₃)₅]₂Cl₂, and Ti[η⁵-C₅(CH₃)₅]₂Cl, have enabled derivation of titaniumcarbon and titaniumchlorine stepwise bond dissociation enthalpies in these species.     

Hydrothermal Synthesis and Up‐conversion Luminescence of Ho3+/Yb3+ Co‐doped PbTiO3

Ho³⁺/Yb³⁺ co‐doped PbTiO₃ nanocrystals with different content of dopant were successfully prepared via a facile hydrothermal method. The purity, morphology, element distribution, chemical state and up‐conversion (UC) photoluminescence (PL) of PbTiO₃ nanocrystals affected by Ho³⁺ dopant are investigated systematically. X‐ray diffraction (XRD) results illustrate that PbTiO₃ samples with the doping Ho³⁺ concentration ranging from 0 to 5 mol‐% are perovskite structure. The doping Ho³⁺ ions have no change on the crystal structure of perovskite PbTiO₃. Owing to the non‐equivalent substitution of Ho³⁺ to Ti⁴⁺ in PbTiO₃, the particle size of Ho³⁺/Yb³⁺ co‐doped PbTiO₃ samples is decreased as well as the particle agglomeration is detected. Moreover, Ho and Yb ions have uniform distributions in the PbTiO₃ nanoparticles as the presence of Ho³⁺ and Yb³⁺ cations. The up‐conversion spectra demonstrate that Ho/Yb co‐doped PbTiO₃ samples have up‐conversion emissions centered at 550 nm, 660 nm and 755 nm, corresponding to the transitions of ⁵F₄(⁵S₂)→⁵I₈, ⁵F₅→⁵I₈ and ⁵S₂(⁵F₄)→⁵I₇ of Ho³⁺ ions. Additionally, the effect of temperature on the UC PL property of Ho³⁺/Yb³⁺ co‐doped PbTiO₃ system is further investigated. The sensitivity and the trend of Ho³⁺/Yb³⁺ co‐doped PbTiO₃ samples in temperature from 298 k to 493K are calculated on the basis of fluorescence intensity ratio (FIR) method. Ho³⁺/Yb³⁺ co‐doped PbTiO₃ nanocrystals are verified the high potential in the optical temperature sensing.     

Zur kenntnis der cyclopentadienyl-nitrosyl-carbonyl-isonitril-komplexe der VI. Und der cyclopentadienyl-dicarbonyl-isonitril-komplexe der VII. Nebengruppe

The nitrosylcarbonylisonitrile complexes η⁵-C₅H₅M(NO)(CO)CNR (R = Me for Cr, Mo, W; R = Et, SiMe₃, GeMe₃, SnMe₃ for Mo) are formed by treatment of the nitrosylcarbonylcyanometalates Na[η⁵-C₅H₅M(NO)(CO)CN] with [R₃O]BF₄ (R = Me, Et), Me₃SiCl, Me₃GeCl or Me₃SnCl. The isoelectronic dicarbonylisonitrile compounds η⁵-C₅H₅Mn(CO)₂CNR (R = SiMe₃, GeMe₃, SnMe₃, PPh₂, AsMe₂) and η⁵-C₅H₅Re(CO)₂CNAsMe₂ are obtained by analogous reactions of Na[η⁵-C₅H₅M(CO)₂CN] (M = Mn, Re) with Me₃ECl (E = Si, Ge, Sn), Ph₂PCl and Me₂AsBr.With phosgene the anionic complexes Na[η⁵-C₅H₅M(CO)₂CN] (M = Mn, Re) can be transformed into the new carbonyldiisocyanide-bridged dinuclear complexes η⁵-C₅H₅M(CO)₂CN-C(O)-NC(OC)₂M-η⁵-C₅H₅. Finally, the reactions of η⁵-C₅H₅M(NO)(CO)CNMe (M = Cr, Mo, W) with NOPF₆, leading to the cationic dinitrosylisonitrile complexes [η⁵-C₅H₅M(NO)₂CNMe]⁺, are described.     

Darstellung und chemie von Me2TlN(SiMe3)2 und Tl[N(SiMe3)2]3

The complexes [Rh(η³-C₃H₄R)(η⁵-C₅R′₅)L]⁺BF₄^- (R  1-Me, R′  H, Me; R  2-Me, R′  H) (L  C₅H₅N, Ph₃P, Ph₃As) have been prepared from Rh(η³-C₃H₄R)(η⁵-C₅R′₅)Cl and AGBF₄ in acetone, followed by reaction with the stoicheiometric quantity of L. The ¹H and ¹³C NMR spectra of the salts are reported and discussed.     

Line-Pro le Analysis of Excitation Spectroscopy in the Even 3p5(2P1/2)nl'[K']J(l'=1,3) Autoionizing Resonances of Ar

The even-parity autoionizing resonance series 3p⁵np'[3/2]_1,2, 3p⁵np'[1/2]₁, and 3p⁵nf'[5/2]₃ of Ar have been investigated exciting from the two metastable states 3p⁵4s[3/2]₂ and 3p⁵4s'[1/2]₀ in the photon energy range of 32500-35600 cm^-1 with an experimental bandwidth of ~0.1 cm^-1. The excitation spectra of the even-parity autoionizing resonance series show typical asymmetric line shapes. New level energies, quantum defects, line profile index and resonance widths, resonance lifetime and reduced widths of the autoionizing resonances are derived by a Fano-type line-shape analysis. The line profile index q and the resonance widths Γ are shown to be approximately proportional to the effective principal quantum number n^*. The line separation of the 3p⁵np' autoionizing resonances is discussed.