19394-85-5

Upstream product

• 136379-31-2 trans-tricarbonyl(fluoro)bis(triphenylphosphine)rhenium 
• 21050-13-5 bis(triphenylphosphine)iminium chloride 
• 7440-66-6 zinc 
• 14099-01-5 rhenium(I) pentacarbonyl chloride 
• 603-36-1 triphenylantimony 
• 118228-22-1 mer,trans-Re(CO)3(PPh₃)2CHO 
• 29857-52-1 trans-trichloro(ethylimido)bis(triphenylphosphine)rhenium(V) 
• 7647-01-0 hydrogenchloride 
• 56-34-8 tetraethylammonium chloride 
• 121-44-8 triethylamine 
• 603-35-0 triphenylphosphine 
• 59751-32-5 [Re(CO)₂(OAc)(PPh₃)₂] 

Downstream Products

• 25734-54-7 trans-mer-Re(H)(PPh₃)2(CO)3 
• 1380170-47-7 cis,mer-ReCl(CO)2(((PPh₂CH₂CH₂)2P)C₆H₄C(C₄NMe₂Et))2BMe₂) 
• 88250-58-2 Re(CO)2(PPh₃)2(OCHNC₆H₄Me-p) 
• 128138-29-4 Re(CO)2(P(C₆H₅)3)2(SC(OC₂H₅)S) 
• 77759-71-8 [Re(CO)2[CH(NC₆H₄p-Cl)](PPh₃)2] 
• 77759-74-1 [Re(CO)2[N(NC₆H₄p-Cl)](PPh₃)2] 
• 88250-60-6 Re(CO)2(P(C₆H₅)3)2(ClC₆H₄NCHO) 
• 88250-59-3 Re(CO)2(P(C₆H₅)3)2(C₆H₅NCHO) 
• 88250-56-0 Re(CO)2(P(C₆H₅)3)2(CH₃C₆H₄NCHO) 
• 88250-61-7 Re(CO)2(P(C₆H₅)3)2(CH₃OC₆H₄NCHO) 
• 88250-62-8 Re(CO)2(P(C₆H₅)3)2(NO₂C₆H₄NCHO) 
• 51406-11-2 Re(CO)2(η3-1,1,1-tris(diphenylphosphino)ethane)Cl 
• 42584-07-6 tricarbonylchlorobis(triphenylphosphine)rhenium(II) tetrafluoroborate 
• 136921-71-6 fac-Re(CO)3(PPh₃)2(OSO₂CF₃) 

Relevant academic research and scientific papers

ReOCl3(PPh3)2] as a substrate for the synthesis of the rhenium(I) carbonyl complexes [Re(CO)2(OAc)(PPh 3)2] and [ReCl(CO)3(PPh3) 2

New preparative methods have been developed for the synthesis of the rhenium(I) carbonyl complexes [Re(CO)2(OAc)(PPh3) 2] (1) and [ReCl(CO)3(PPh3)2] (2). Acetic anhydride was decarbonylated during the course of its reaction with [ReOCl3(PPh3)2], resulting in the formation of the rhenium(I) carbonyl complex [Re(CO)2(OAc)(PPh3) 2] (1), which was subsequently converted almost quantitatively to [ReCl(CO)3(PPh3)2] (2) via the decarbonylation of its acetate group under acidic conditions.

Preparation and reactivity of the heterobimetallic ReIr face-shared bioctahedral compounds Cp*Ir(μ-Cl)3Re(CO)3 and Cp*Ir(μ-SC6H4Me-4)3Re(CO) 3: X-ray diffraction structures and redox behavi

Thermolysis of the dinuclear compound [Cp*IrCl2]2 (1) with ClRe(CO)5 (2) leads to the formation of the confacial bioctahedral compound Cp*Ir(μ-Cl)3Re(CO)3 (3) in high yield. Whereas the substitution o

Chemistry of coordinated nitroxyl. Reagent-specific protonations of trans-Re(CO)2(NO)(PR3)2 (R = Ph, Cy) that give the neutral nitroxyl complexes cis,trans-ReCl(CO)2(NH=O)(PR3)2 or the cationic hydride complex [trans,trans-ReH(CO)2(NO)(PPh3)2 +][SO3CF3-]

The reactions of hydrochloric and triflic acids with the five-coordinate nitrosyl complexes trans-Re(CO)2(NO)(PR3)2 (2a, R = Ph; 2b, R = Cy) have been investigated. Reaction of anhydrous HCl with 2 results in a formal protonation of the nitrosyl ligand and addition of chloride to the metal, giving the neutral nitroxyl complex cis,trans-ReCl(CO)2(NH=O)(PR3)2 (3a, R= Ph; 3b, R = Cy). Reaction of Bronsted bases with 3a or 3b results in clean conversion of 3 to 2 when the base is appropriately strong (pKb ? 7). Addition of HOSO2CF3 to solutions of 2a results in protonation at the metal and formation of the cationic rhenium hydride [trans,trans-ReH(CO)2(NO)(PPh3)2 +][SO3CF3-] (4) in 74% yield; the deuteride [trans, trans-Re(2H)(CO)2(NO)(Pph3)2 +][SO3CF3-] (4-d) was analogously prepared from 2HOSO2CF3. 4 crystallized from CH2Cl2/Et2O solution in the orthorhombic space group Pnma, with a = 17.2201(2) A, b = 23.6119(3) A, c = 9.2380(2) A, and Z = 4. The least-squares refinement converged to R(F) = 0.039 and R(wF2) = 0.063 for the 4330 unique data with I > 2σ(I). The structure of 4 shows that the hydride (Re - H = 1.74 A) occupies the position trans to the linear nitrosyl ligand (Re - N - O = 178.1(4)°) in the pseudooctahedral complex cation. Complex 4 does not react with chloride to give 3a. DFT calculations carried out on free nitroxyl and its model complexes [Re(CO)5(NH=O)+] (5), [mer, trans-Re(CO)3(NH=O)(PH3)2+] (6), and cis,trans-ReCl(CO)2(NH=O)(PH3)2 (7) indicate that coordinated nitroxyl acts as both a σ-donor and π-acceptor ligand, consistent with the observed trend for ν(NO) in free HN=O (1563 cm-1), [mer,trans-Re(CO)3(NH=O)(PPh3)2+] (1, 1391 cm-1), 3a (1376 cm-1), and 3b (1335 cm-1).

Oligophosphan-liganden XLII. Carbonyl(cyclopentadienyl) rheniumt(I) -Komplexe η1-C5H5Re(CO)3L2 mit fluktuierender sp3-und starrer sp2-Koordination des C5H5-rings1,2

Combination of the halo rhenium(I) complexes fac-Re(CO)3L2X (L/X = PMe3/Br (1), PPh3/Cl (2), PCy3/Br (3)), fac-Re(CO)3(Ph2PCH2PPh2)Br, 4, fac-Re(CO)3[Ph2P(CH2)2PR2]Br (R = Me (5), Ph (6), Cy (7)), fac-Re(CO)3[Ph2P(CH2)3PPh2]Cl, 8, and fac-Re(CO)3[C5H8(PCy2)2]Br, 9 (C5H8(PCy2)2 = rac,trans-cyclopentan-1,2-diyl-bis(dicyclohexyl)phosphine), with Ag[O3SCF3] yielded fac-Re(CO)3(PR3)2OSO2CF3 (R = Me (10), Ph (11), Cy (12)), fac-Re(CO)3[R2P(CH2)nPR2]OSO2CF3 (n-1: R = Ph (13); n = 2: R = Me (14), Ph (15), Cy (16); n = 3: R = Ph (17)), and fac-Re(CO)3[C5H8(PCy2)2]OSO2CF3, 18. Triflates 10, 11, and 14-17 were converted into cyclopentadienyl derivatives containing fluxional sp3-bonded C5H5 rings,fac-η1-C5H5Re(CO)3(PMe3)2, 19, fac-η1-C5H5Re(CO)3[R2P(CH2)nPR2] (n = 2: R = Me (20), Ph (21), Cy (22); n = 3: R = Ph (23)), and mer,trans-η1-C5H5Re(CO)3(PPh3)2, 24, when allowed to interact with Na[C5H5] in THF. Treatment of 18 with Na[C5H5] produced fac-η1-C5H5Re(CO)3[C5H8(PCy2)2] as a mixture of three isomers with the rhenium atom in the allylic position of a fluxional sp3-bonded rings (25a) or in the two vinylic sites of an sp2-bonded rigid C5H5 system, where the CH2 group is either α or β to the metalated carbon atom (25b, 25c). η5-C5H5Re(CO)3 and fac-[Re(CO)3(Ph2PCH2PPh2-P,P′)(Ph2PCH2PPh2-P)]+ were identified as the only organometallic complexes resulting from interaction of triflates 12 and 13 with Na[C5H5]. The structure of fac-η1-C5H5Re(CO)3[Ph2P(CH2)2PPh2] -2CH2Cl2 was determined by single-crystal X-ray diffractometry.

Electronic Emission and Absorption Spectroscopy of the Rhenium Complexes Re(CO)3Cl(Phosphine)2

The compounds Re(CO)3Cl(L)2, L = triphenylphosphine, tri-p-tolyphosphine, and Re(CO)3Cl(L'), L' = 1,2-bis(diethylphosphinoethane) are luminescent in solution and in crystalline form when excited between 351 nm and 514 nm at temperatures ranging from 10 K to room temperature.The absorption spectra contain a weak (E ca. 10 M-1 cm-1) band in the visible region of the spectrum between 400 and 500 nm.The lowest energy transition giving rise to these spectroscopic features is assigned to a d-d transition. - Keywords.Rhenium complexes; Electronic emission; Absorption.

A Re(I)-Re(VII) COMPLEX BY THE OXYGENATION REACTIONS OF Re(I) SPECIES. REACTIVITY AND X-RAY STRUCTURAL CHARACTERIZATION OF Re(CO)3(PPh3)2(OReO3)

The hydrido complex HRe(CO)2(PPh3)3 reacts with tertiary amines, in the presence of O2 and H2O, to give Re(CO)2(PPh3)2(O2CR), containing a chelating carboxylato group originated by oxidation of the alkyl group of the amine.NEt3, N(n-Pr)3 and N(n-Bu)3 have been used, the acetato, propionato and butyrato derivatives being respectively obtained.In the absence of the amine, the reaction gives the Re(I)-Re(VII) complex Re(CO)3(PPh3)2(OReO3), 1, containing a coordinated perrhenate ion.The same species was obtained by reaction of Re(CO)2(PPh3)2(NHCOC6H4Me) with O2/H2O.Complex 1 has been alternatively prepared by reacting ReCl(CO)3(PPh3)2 with AgReO4.Crystals of 1 have been shown by single crystal X-ray analysis to be monoclinic, space group P21/n (No. 14) with a = 10.248(6), b = 27.487(5), c = 13.247(2) Angstroem, β = 97.55(2) deg and Z = 4.The refinement performed by full-matrix least-squares methods, for 4651 independent significant reflections, gave a final R value of 0.029.The crystals contain discrete dinuclear molecules with an octahedrally coordinated Re(I) atom bearing three carbonyls, two mutually trans triphenylphosphine ligands and a coordinated ReO4- moiety.Complex 1 was shown to be partially dissociated in acetone solution and the value of the dissociation constant has been estimated by means of the Ostwald relationship -5>.The addition of NEt3 to an acetone solution of 1 at room temperature causes its complete dissociation.Complete dissociation was also observed in acetonitrile, with formation of the ionic species , 2.Complex 1 reacts with NEt3, at 55 deg C under an inert atmosphere, to give the rhenium(I) acetato derivative Re(CO)2(PPh3)2(O2CCH3), showing that the perrhenate anion is able to perform the oxidation of alkyl groups of tertiary amines to carboxylato groups.

Separating the Re-H and H-H dipole-dipole contributions to the 1H NMR spin-lattice relaxation rate of the hydride ligand in mer,trans-ReH(CO)3(PPh3)2 by deuteration

The reaction of mer,trans-ReCl(CO)3(PPh3)2 with LiAlH4 in THF at room temperature gives mer,trans-ReH(CO)3(PPh3)2 (1). The temperature dependence of the 1H NMR spin-lattice (T1) relaxation rate of the hydride resonance of 1 is studied to try to understand the excess T1 relaxation often found for rhenium hydride complexes. Our previous assumption that the dipole-dipole relaxation mechanism is dominant is confirmed. Two main dipole-dipole contributions are identified. One is from the usual proton-proton dipole-dipole (HHDD) relaxation between the hydride ligand and the protons of the phosphine ligands, and the other from the rhenium-hydride dipole-dipole (ReHDD) relaxation. The two contributions can be separated by studying mer,trans-ReH(CO)3(PPh3-d15)2 (1-d30). The two components come to a minimum T1 value at different temperatures. The T1(min) value observed for the ReHDD relaxation in 1-d30 is consistent with an Re-H bond distance of 1.75 ?, which is in satisfactory agreement with those determined by neutron diffraction studies on other rhenium hydride complexes.

Synthesis and reactivity of trans-ReF(CO)3(PPh3)2 and trans-(Me3SiO)3V≡NRe(CO)3(PPh 3)2

The d6 fluoro complex trans-ReF(CO)3(PPh3)2 (1) has been prepared in good yield by reaction of trans-ReCl(CO)3(PPh3)2 (2) with Ag(SO3CF3) followed by [N(PPh3)2]F. Addition of 2 equiv of [N(PPh3)2]Cl to 1 affords not the expected simple anion-metathesis equilibrium, but a mixture containing 2 as well as other species. The lability of 1 toward carbonyl exchange with 13CO and toward reaction with NCS- has been examined and is far greater than that for 2. Compound 1 reacts with V(NSiMe3)(OSiMe3)3 (4) to form Me3SiF and trans-(Me3SiO)3V≡NRe(CO)3(PPh 3)2 (5), whereas no reaction is observed upon addition of the chloro complex 2 to 4. Reaction of 5 with Me3SiCl cleanly substitutes chlorides for the trimethylsiloxy groups on vanadium to generate trans-Cl3V≡NRe(CO)3(PPh3)2 (6), with no evidence for the expected cleavage of the nitride bridge to yield 2 and 4. Spectroscopic and solution properties of this series of compounds and comparisons of the fluoro complex (1) with its heavier halo analogues are presented.

Synthesis and thermolysis of neutral metal formyl complexes of molybdenum, tungsten, manganese, and rhenium

The possible intermediacy of catalyst-bound formyls in syngas transformations has prompted efforts to prepare and study the chemistry of transition-metal formyl complexes over more than a decade. We have used a mild borohydride in our reactions with metal carbonyl cations and have introduced some variations into the syntheses which allow, in almost all cases, for the pure formyl complex to be precipitated from solution as it is formed. The formyl complexes and their cationic precursors are shown. Seven of the formyls are new; improved procedures have been established for the other four. All but one of the compounds have been isolated.