Reaction Of Rhenium Research Articles

Azobased iminopyridine ligands and their rhenium metal complexes: Syntheses, spectroscopic, trans-cis photoisomerization and theoretical studies

The reaction of rhenium(I) pentacarbonyl chloride Re(CO)5Cl with N,N-dimethyl-4-((E)-(pyridin-2-ylmethylene) amino)phenyl) diazenyl) aniline L1 and (E)-4-((E)-(4-nitrophenyl)diazenyl)-N-(pyridin-2-ylmethylene) aniline L2 affords two rhenium metal complexes [ReL1(CO)3Cl] (ReL1) and [ReL2(CO)3Cl] (ReL2), respectively. These Re(I) complexes were characterized in detail, including their single crystal structures, absorption spectra and electronic structures using DFT calculations. Trans to cis photoisomerization of the free ligands and complexes was investigated experimentally and rationalized theoretically. Interestingly, light-induced photoisomerization of the azo fragment is observed for free ligand L1 while inhibition of this process is produced upon coordination to Re metal cation.

Kinetics of the single-electron chemical oxidation of rhenium(V) meso-phenyl-β-octaethylporphyrinate

The states and reactions of rhenium(V) complexes with meso-monophenyl-β-octaethylporphines containing Cl− and OPh− as axial ligands O=Re(Cl)MPOEP and O=Re(OPh)MPOEP in concentrated sulfuric acid at 298–348 K are studied via spectral and kinetic methods. While stable along M-N bonds, O=Re(Cl)MPOEP is found to undergo slow oxidation after transforming into axial hydrosulfate complex O=Re(HSO4)MPOEP. It is shown that the sole electron oxidizing agent is atmospheric oxygen (with the assistance of highly concentrated protons) and the sites of reduction are aromatic ligands. The reaction product was identified as π-radical cation O=Re(HSO4)MPOEP·+. Forward and inverse chemical kinetics solutions are used to obtain a full kinetic equation and the reaction rate parameters of elementary steps, and to establish the stoichiometric mechanism of the composite oxidation of the complex. Complex O=Re(OPh)MPOEP in the form O=Re(OPh)(O2)MPOEP with coordinated oxygen is shown experimentally to be stable with respect to oxidation. The obtained results are important for identifying intermediates in processes catalyzed by stable metal porphyrins.

Composition and structure of rhenium(VI) complexes as found by EPR and laser mass spectrometry

Reactions of rhenium with oxymonothiophenols in ReO4−-HCl (H2SO4)-L systems (where L is 3-tert-butyl-2-mercaptophenol or 3-tert-butyl-2-mercapto-6-methylphenol) to form complexes, in which rhenium has an oxidation number of +6, have been studied by means of electron paramagnetic resonance (EPR), spectrophotometry, and surface-assisted laser desorption/ionization methods. The parameters of EPR spectra have been determined, and ion peaks in the mass spectra have been identified. It has been found that the studied complexes are octahedrons distorted in the equatorial plane and the composition of compounds satisfies the Re: L ratio of 1: 3.

Syntheses, structures, and reactions of rhenium and ruthenium carbonyl derivatives of 2,2′-bis(indenyl)propane

Treatment of 2,2′-bis(indenyl)propane with Re2(CO)10 in refluxing decane resulted in both monometalated rhenium carbonyl complex 1 and bimetalated rhenium carbonyl derivatives rac-2 and meso-2, which were separated by chromatography, and fully characterized by 1H NMR, IR, EA and single crystal X-ray diffraction. UV photolysis of 1 yielded the novel compound (CMe2)[(η5-C9H6)(η2-C9H7)]Re(CO)2 (3), in which one carbonyl ligand is replaced by an η2 coordinated isomerized pendant indene group. Heating a mixture of 2,2′-bis(indenyl)propane with Ru3(CO)12 in refluxing decane provided the corresponding diruthenium carbonyl complexes as a mixture of rac and meso diastereomers (rac-5, and meso-5), which were also successfully separated and characterized by X-ray diffraction.

The Reaction of Rhenium(V) Cores with a Tetradentate Schiff Base. The Isolation of '3+3' and '4+0' Complexes of Rhenium(V)

The reaction of the potentially tetradentate N4-donor ligand N,N?-bis[(2-aminophenyl)methylidene]ethane-1,2-diamine (H2ane) with various rhenium(V) precursors led to the formation of different rhenium(V) complexes. With trans-[ReOBr3(PPh3)2], the unusual ?3+3' complex cation [Re(tnn)(Htnn)]2+ (H2tnn = N-(2-aminophenylmethylidene)ethane-1,2-diamine) was isolated. With trans-[ReO2(py)4]Cl, the complex [ReO(dne)] was found (H3dne = N1-2-aminobenzyl-N2-2-aminobenzylideneethane-1,2-diamine), and the cationic complex [ReO(ane)]+ was formed from cis-[ReO2I(PPh3)2]. These products were characterized by 1H NMR and IR spectroscopy, and by X-ray diffraction.

Reactions of rhenium and manganese carbonyl complexes with 1,8-bis(diphenylphosphino)naphthalene: Ligand chelation, C–H and C–P bond-cleavage reactions

Reaction of [Re 2(CO) 8(MeCN) 2] with 1,8-bis(diphenylphosphino)naphthalene (dppn) afforded three mono-rhenium complexes fac-[Re(CO) 3(κ 1:η 1-PPh 2C 10H 6)(PPh 2H)] ( 1), fac-[Re(CO) 3{κ 1:κ 1:η 1-(O)PPh 2C 10H 6(O)PPh(C 6H 4)}] ( 2) and fac-[ReCl(CO) 3(κ 2-PPh 2C 10H 6PPh 2)] ( 3). Compounds 1– 3 are formed by Re–Re bond cleavage and P–C and C–H bond activation of the dppn ligand. Each of these three complexes have three CO groups arranged in facial fashion. Compound 1 contains a chelating cyclometalated diphenylnaphthylphosphine ligand and a terminally coordinated PPh 2H ligand. Compound 2 consists of an orthometalated dppn-dioxide ligand coordinated in a κ 1:κ 1:η 1-fashion via both the oxygen atoms and ortho-carbon atom of one of the phenyl rings. Compound 3 consists of an unchanged chelating dppn ligand and a terminal Cl ligand. Treatment of [Mn 2(CO) 8(MeCN) 2] with a slight excess of dppn in refluxing toluene at 72 °C, gave the previously reported [Mn 2(CO) 8(μ-PPh 2) 2] ( 4), formed by cleavage of C–P bonds, and the new compound fac-[MnCl(CO) 3(κ 2-PPh 2C 10H 6PPh 2)] ( 5), which has an unaltered chelating dppn and a terminal Cl ligand. In sharp contrast, reaction of [Mn 2(CO) 8(MeCN) 2] with slight excess of dppn at room temperature yielded the dimanganese [Mn 2(CO) 9{κ 1-PPh 2(C 10H 7)}] ( 6) in which the diphenylnaphthylphosphine ligand, formed by facile cleavage of one of the P–C bonds, is axially coordinated to one Mn atom. Compound 6 was also obtained from the reaction of [Mn 2(CO) 9(MeCN)] with dppn at room temperature. The XRD structures of complexes 1– 3, 5, 6 are reported.

Synthesis, Characterization and Luminescence Studies of Trinuclear Rhenium–Cobalt Mixed-Metal Alkynyl Complexes Containing a Tetrahedral Co2C2Cluster Unit

The reaction of rhenium(I) diynyl complexes [Re(CO)3(N–N)(C≡C--C≡CH)] [N–N = tBu2bpy (1), bpy (2)] with Co2(CO)8 in THF yielded a new class of luminescent trinuclear rhenium–cobalt mixed-metal alkynyl complexes, [Co2{μ-HC2C≡C[Re(CO)3(N–N)]}(CO)6] [N–N = tBu2bpy (3), bpy (4)]. Their luminescence and electrochemical properties have also been studied.

Synthesis and Reactions of Rhenium(V) Oxo−Hydride Complexes

Tp*ReO(H)Cl, TpRe(O)H(Cl), and Tp*ReO(H)2 have been prepared by alkoxide-for-hydride metathesis using BH3·THF. The triflate derivative Tp*Re(O)H(OTf) inserts olefins and is oxidized by oxygen-atom ...

Synthesis and Characterization of Rhenium(VI) cis-Dioxo Complexes and Examination of Their Redox Chemistry.

Reaction of rhenium(V)-oxo-halo-triflate complexes (HB(pz)(3))ReO(X)OTf (1, X = Cl, Br, I) with 1 equiv of pyridine N-oxide forms rare d(1) rhenium(VI) cis-dioxo compounds (HB(pz)(3))ReO(2)X (2, X = Cl, Br, I). This reaction likely occurs by initial formation of the d(0) rhenium(VII) dioxo cation (HB(pz)(3))ReO(2)X(+) by oxygen atom transfer, followed by a rapid one electron reduction. The chloride derivative 2a has been characterized by an X-ray crystal structure. The d(1) dioxo compounds are fairly stable, disproportionating slowly to (HB(pz)(3))ReO(3) and (HB(pz)(3))ReOX(2). Electrochemical oxidations of (HB(pz)(3))ReO(2)X to Re(VII) cations are reversible and are at remarkably high potentials (E(1/2) = 0.93 V vs Cp(2)Fe(+/0) in acetonitrile for 2a). When Me(2)SO is used as the oxidant instead of pyridine N-oxide, the Re(V) adducts [(HB(pz)(3))ReO(X)(OSMe(2))][OTf] (5) are formed by triflate displacement. These complexes reversibly lose SMe(2) (for 5a, k = 3.3(4) x 10(-)(6) s(-)(1) at 297 K in CD(2)Cl(2)), as shown by isotope exchange experiments. The intermediate Re(VII) cations (HB(pz)(3))ReO(2)X(+) oxidize Me(2)S much faster than Me(2)SO, indicating that they are highly electrophilic oxygen atom transfer reagents. Complexes 2, however, are relatively unreactive materials. Crystallographic data for 2a: C(9)H(10)BClN(6)O(2)Re; monoclinic, Cc; a = 14.716(3), b = 7.651(2), c = 13.232(3) Å; beta = 110.61(3) degrees; Z = 4.

Preparation and reactions of rhenium(VII) trioxo hydrogendiolato complexes and rhenium(VI) oxo bis(diolato) complexes

The compound Re2O7, Re2O7·2H2O or [ReO3(OSiMe3)] reacted with H2diol to form complexes having the general formula [ReO3(Hdiol)] where H2diol = 2,3-dimethylbutane-2,3-diol (H2pin) or 1,1′-bicyclohexane-1,1′-diol (H2bicy). In the case of H2pin the complex [ReO3(Hpin)]·H2pin is formed initially in the reaction of rhenium(VII) oxides with an excess of pinacol. The hydrogen bonded free pinacol molecule can be removed by sublimation. The monomethyl derivative of pinacol, HMepin, reacts in a similar way to form the complex [ReO3(Mepin)]. In the rhenium(VII) compounds the Re atom has a distorted trigonal bipyramidal co-ordination geometry. Pale yellow solutions of [ReO3(Hdiol)] in CH2Cl2 slowly become orange and red crystals having the formula [ReO(diol)2] may be isolated. The reaction of rhenium(VII) oxides with H2diol and PPh3 in the presence of drying agents in CH2Cl2 produced the same compounds in high yield. The crystal structures of the rhenium(VI) complexes reveal that the rhenium(VI) cations have square pyramidal co-ordination geometries. The rhenium(VI) oxo bis(diolato) complexes are thermally stable and do not readily undergo oxidation in dry air.

Sulfur–carbon bond cleavage in reactions of rhenium(V) complexes of NS3 ligands with tertiary phosphines: crystal and molecular structures of [ReO(SCH2CH2NCOCH2S)(PMe2Ph)] and [ReO(SCMe2CH2NCOCH2SCH2CH2S)(PMePh2)

The neutral rhenium(V) oxo complex [ReO{S(CH2)2SCH2CONCH2S}] reacted with tertiary phosphines PMe2Ph or PMePh2 to give the rhenium(V) species [ReO(NS2)(PR′3)] (PR′3 = PMe2Ph 1, or PMePh2 2), with loss of a SCH2CH2 group. The introduction of dimethyl substituents at C(6) of the tetradentate ligand prevents C–S bond cleavage and [ReO(NS2)(PR′3)] type complexes were formed (PR′3 = PMe2Ph 3, or PMePh2 4). The crystal and molecular structures of complexes 1 and 4 have been determined. Complex 1 is essentially square pyramidal with an apical oxo group and a PNS2 donor set in the basal sites. The geometry of 4 is essentially octahedral with a thiolate sulfur of the NS3 ligand trans to the oxo group.

Reactions of Rhenium(V) Oxo and Nitrido Complexes with 1-Phenyl-2-(diphenylphosphino)ethanone (P⌒OH). Synthesis and Crystal Structure of ReOCl(P⌒O)2and ReN(PPh3)(P⌒O)2

Structurally related six-coordinated oxo ReOCl(P⌒O)2 and nitrido ReN(PPh3)(P⌒O)2 complexes were synthesized. The bidentate P⌒O- ligand forms oxo ReOCl(P⌒O)2 and nitrido ReN(PPh3)(P⌒O)2 complexes containing quasi-isostructural ReO(P⌒O)2 and ReN(P⌒O)2 units. The Cl site in the oxo compound is occupied by PPh3 in the nitride. PPh3 is smoothly displaced in solution by pyridine, 1-methylimidazole, and P(p-tolyl)3 with retention of stereochemistry.

Half-sandwich rhenium(III) acyl complexes: synthesis, structure and conversion to rhenium(I) and rhenium(III) isonitrile complexes

The synthesis, structure and reactions of rhenium(III)η 1-acyl complexes bearing a cyclopentadienyl (Cp) or a pentamethylcyclopentadienyl (Cp *) ligand are described. Oxidation of the rhenium(I) acyl complexLi[CpRe(CO) 2(η 1-PhCO)] ( 1) with one equivalent of PhICl 2 affords the rhenium(III) acyl complex trans-CpRe(CO) 2(η 1-PhCO)Cl ( trans- 2a). The diphenylcarbene complex Cp(CO) 2Re CPh 2 ( 3) is also formed in this reaction. Similarly, oxidation of 1 with Br 2 givescis/trans-CpRe(CO) 2(η 1-PhCO)Br(cis/trans- 2b), which can also be obtained from the alkoxycarbene complex Cp(CO) 2Re C(OEt)Ph ( 4) with one equivalent of Br 2. Oxidation ofLi[Cp *Re(CO) 2(η 1-PhCO)] ( 5) with one equivalent of PhlCl 2, Br 2 or I 2 affords selectively the rhenium(III) acyl complexescis/trans-Cp *Re(CO) 2(η 1-PhCO)X(X Cl I) [ cis/trans-( 6a–6c)]. Cleavage of the Re C acyl bond of trans- 2a with PhICl 2 and of cis/trans- 2b with Br 2 offers a convenient way to the rhenium(III) dihalo complexes cis/trans-CpRe(CO) 2Cl 2 ( cis/trans- 7a) and cis/trans-CpRe(CO) 2Br 2 ( cis/trans- 7b) respectively. Reduction of cis/trans- 7a with sodium/amalgam gives in the presence of RNC, the rhenium(I) isonitrile complexes CpRe(CO) 2(CNR) ( 8:R Et; 9:R 10:R 1Bu). Oxidation of 8–10 with one equivalent of bromine leads selectively to the rhenium(III) isonitrile complexes [ trans-CpRe(CO) 2(CNR)Br]Br ( 11:R = Et; 12:R - iPr; 13:R = tBu). The crystal structure of the acyl complex trans- 2b and the carbonyl complex [Cp 2 *Re 2(CO) 4(μ-Br)][Re 2(μ-Br) 3(CO) 6] ( 14) are described, complex 14 being formed by the thermal decomposition of cis/trans- 6b.

Cl3Ga–NReCl2(PMe2Ph)3] and [Cl3Ga–NReCl(PMe2Ph)3(NCMe)][GaCl4]: the first complexes with nitrido bridges between main group and transition metals

Almost linear nitrogen bridges between rhenium and gallium are formed during the reaction of rhenium(V) complexes containing terminal ‘N3–’ ligands with gallium trichloride.

The Crystal Structures of Re2Al, Re4Al11, and ReAl6

Well-crystallized samples of the rhenium aluminides Re4Al11 and ReAl6 were obtained by reaction of rhenium with an excess of aluminum. Re4Al11 was found to be isotypic with Mn4Al11. The MnAl6 type structure of ReAl6 was confirmed. The crystal structures of both compounds were refined from single-crystal X-ray data. Re4Al11:P1̄, Z = 1, a = 516.0(1) pm, b = 896.3(2) pm, c = 516.9(1) pm, a = 90.44(1)°, β = 99.76(1)°, γ = 105.17(1)°, V = 0.2271 nm3, R = 0.036 for 2315 structure factors and 74 variable parameters. ReAl6: Cmcm, Z = 4, a = 761.0(1) pm, b = 660.5(1) pm, c = 903.4(1) pm, V = 0.4541 nm3, R = 0.013 for 711F values and 23 variables. In both structures the rhenium atoms have ten aluminum neighbors at distances from 245 to 277 pm. The Al-Al distances cover the whole range from 251 to 362 pm rather continuously. The previously reported compound Re2Al with the tetragonal MoSi2-type structure has the lattice constants a = 298.1(1) pm, c = 958.4(4) pm, V = 0.08519 nm3. ReAl6 shows Pauli-paramagnetism.

The redox behaviour of rhenium—VIII[1,2]. Some observations on the reactions of rhenium(IV) iodide with tertiary amines and phosphines

The redox behaviour of rhenium—VIII[1,2]. Some observations on the reactions of rhenium(IV) iodide with tertiary amines and phosphines

Reactions of rhenium and other refractory metals with some metal-like compounds

Reactions of rhenium and other refractory metals with some metal-like compounds

The reaction of rhenium(III) chloride with anhydrous liquid ammonia

The reaction of rhenium(III) chloride with anhydrous liquid ammonia

Redox behavior of rhenium halides. IV. Reactions of rhenium(III) chloride with monodentate tertiary amines. Isolation and characterization of a new class of rhenium(II) derivatives

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTRedox behavior of rhenium halides. IV. Reactions of rhenium(III) chloride with monodentate tertiary amines. Isolation and characterization of a new class of rhenium(II) derivativesD. G. Tisley and R. A. WaltonCite this: Inorg. Chem. 1973, 12, 2, 373–378Publication Date (Print):February 1, 1973Publication History Published online1 May 2002Published inissue 1 February 1973https://doi.org/10.1021/ic50120a027RIGHTS & PERMISSIONSArticle Views161Altmetric-Citations38LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (865 KB) Get e-Alerts Get e-Alerts

Polytertiary phosphines and arsines. VI. Some metal complexes of the mixed phosphine-diarsine bis(2-diphenylarsinoethyl)phenylphosphine

The following metal complexes of the phosphine-diarsine [(C 6H 5) 2AsCH 2CH 2] 2PC 6H 5 (abbreviated as AsfPfAsf) can be prepared by procedures analogous to the preparation of the corresponding complexes of the the triphosphine [(C 6H 5) 2PCH 2CH 2] 2PC 6H 5: ( 1) Monoligate monometallic (AsfPfAsf)Fe(CO) (COCH 3)(C 5H 5); ( 2) Biligate monometallic (AsfPfAsf)M(CO) 4 (M = Cr and Mo) and [C 5H 5Mo(CO) 2(AsfPfAsf)][PF 6]; ( 3) Triligate monometallic [(AsfPfAsf)MCl][PF 6] (M = Pd and Pt), (AsfPfAsf)RhCl 3, (AsfPfAsf)M(CO) 3 (M = Cr and Mo), and (AsfPfAsf)Mn(CO) 2Br. Reaction of rhenium(III) chloride with AsfPfAsf in boiling acetonitrile gives brown (AsfPfAsf) 2Re 3Cl 9. Reaction of osmium tetroxide and hydrochloric acid with AsfPfAsf in boiling ethanol gives the yellow-orange osmium(III) derivative (AsfPfAsf)OsCl 3. Reaction of [Rh(CO) 2Cl] 2 with AsfPfAsf in boiling toluene gives brown sparingly soluble (AsfPfAsf)Rh 2(CO) 3Cl 2. Reaction of CH 3Mo(CO) 3C 5H 5 with AsfPfAsf in acetonitrile at room temperature gives yellow monoligate monometallic (AsfPfAsf)Mo(CO) 2(COCH 3)(C 5H 5) rather than a triligate trimetallic derivative. Similarly the reaction of CH 3Mo(CO) 3C 5H 5 with the phosphine-arsine (C 6H 5) 2AsCH 2CH 2P(C 6H 5) 2 (abbreviated as AsfPf) gives the yellow monometallic derivative (AsfPf)Mo(CO) 2(COCH 3(C 5H 5) rather than a biligate bimetallic derivative.