14099-01-5Relevant articles and documents
THE USE OF SO2Cl2 IN ORGANOMETALLIC CHEMISTRY. CONVENIENT HIGH YIELD SYNTHESES OF AND (M = Mn or Re)
Manning, A. R.,McNally, Gerald,Davis, Reg,Rowland, Christopher C.
, p. C15 - C16 (1983)
Depending on the substrate and the reaction conditions, SO2Cl2 is a useful reagent which brings about either chlorination or the formation of cationic species on reaction with transition metal carbonyl complexes.
Water-soluble carbonyl complexes of 99Tc(I) and Re(I) with adamantane-cage aminophosphines PTA and CAP
Miroslavov, Alexander E.,Britvin, Sergey N.,Braband, Henrik,Alberto, Roger,Stepanova, Ekaterina S.,Shevyakova, Anna P.,Sidorenko, Georgy V.,Lumpov, Alexander A.
, p. 83 - 89 (2019)
Pentacarbonyl complexes of 99Tc and Re [M(CAP)(CO)5]X and [M(PTA)(CO)5]X (M = 99Tc or Re and X = ClO4? or OTf–) with aminophosphine ligands 1,4,7-triaza-9-phosphatricyclo[5.3.214,9]tridecane (CAP) and 1,3,5-triaza-7-phosphaadamantane (PTA) were prepared for the first time by the reaction of [MX(CO)5] (M = 99Tc or Re, X = ClO4? or OTf–) with CAP and PTA in CH2Cl2 at room temperature. The reaction of [TcCl(CO)5] with CAP in refluxing CH2Cl2 yields the tricarbonyl complex [99TcCl(CAP)2(CO)3]. Treatment of [Re(H2O)3(CO)3]Cl with CAP in aqueous solution at 40–50 °C gives the rhenium analog [ReCl(CAP)2(CO)3]. Both penta- and tricarbonyl phosphine complexes were characterized by spectroscopic methods (IR, NMR, MS) and single crystal X-ray diffraction. The [M(PTA)(CO)5]X complexes are soluble in aqueous solutions, whereas their CAP analogs are not. The CAP complexes become water-soluble after acidification with dilute acids. As the pH of their aqueous solutions increases, they start to slowly degrade at pH 8 and completely decompose at pH 14. In acidic media, the pentacarbonyl complexes undergo stepwise protonation and are stable indefinitely.
Direct and high yield syntheses of Re2(CO)10 and Re(CO)5 Cl by sodium reduction of K2ReCl6 under CO
Klahn, A. Hugo,Oelckers, Beatriz,Toro, Adriana,Godoy, Fernando
, p. 121 - 122 (1997)
A convenient procedure for the synthesis of the rhenium carbonyls Re2(CO)10 and Re(CO)5 Cl is reported. Sodium reduction of the easily available K2ReCl6, under CO presssure (2400 psi, 280°C (external temperature), THF as solvent) affords Re2(CO)10 and Re(CO)5Cl in 81% and 86% isolated yield, respectively. Depending on the hexachlororhenate:Na ratio, either carbonyl derivative can be obtained almost exclusively.
Photoactivated in Vitro Anticancer Activity of Rhenium(I) Tricarbonyl Complexes Bearing Water-Soluble Phosphines
Marker, Sierra C.,MacMillan, Samantha N.,Zipfel, Warren R.,Li, Zhi,Ford, Peter C.,Wilson, Justin J.
, p. 1311 - 1331 (2018)
Fifteen water-soluble rhenium compounds of the general formula [Re(CO)3(NN)(PR3)]+, where NN is a diimine ligand and PR3 is 1,3,5-triaza-7-phosphaadamantane (PTA), tris(hydroxymethyl)phosphine (THP), or 1,4-diacetyl-1,3,7-triaza-5-phosphabicylco[3.3.1]nonane (DAPTA), were synthesized and characterized by multinuclear NMR spectroscopy, IR spectroscopy, and X-ray crystallography. The complexes bearing the THP and DAPTA ligands exhibit triplet-based luminescence in air-equilibrated aqueous solutions with quantum yields ranging from 3.4 to 11.5%. Furthermore, the THP and DAPTA complexes undergo photosubstitution of a CO ligand upon irradiation with 365 nm light with quantum yields ranging from 1.1 to 5.5% and sensitize the formation of 1O2 with quantum yields as high as 70%. In contrast, all of the complexes bearing the PTA ligand are nonemissive and do not undergo photosubstitution upon irradiation with 365 nm light. These compounds were evaluated as photoactivated anticancer agents in human cervical (HeLa), ovarian (A2780), and cisplatin-resistant ovarian (A2780CP70) cancer cell lines. All of the complexes bearing THP and DAPTA exhibited a cytotoxic response upon irradiation with minimal toxicity in the absence of light. Notably, the complex with DAPTA and 1,10-phenanthroline gave rise to an IC50 value of 6 μM in HeLa cells upon irradiation, rendering it the most phototoxic compound in this library. The nature of the photoinduced cytotoxicity of this compound was explored in further detail. These data indicate that the phototoxic response may result from the release of both CO and the rhenium-containing photoproduct, as well as the production of 1O2.
A Re(CO)5 fragment bonded to a polyhedral oligomeric hydroxysilsesquioxane as a model which gives further evidence to the existence of an unexpected Re(CO)5 surface species
Lucenti, Elena,D'Alfonso, Giuseppe,Macchi, Piero,Maranesi, Mario,Roberto, Dominique,Sironi, Angelo,Ugo, Renato
, p. 12054 - 12055 (2006)
Reaction of Re(CO)5O3SCF3 with (c-C6H11)7Si8O12O-Li+ at 273 K under a CO atmosphere affords the [Re(CO)5OR] (R = (c-C6H11)7Si8O12) derivative (1). 1 is the first example of a rhenium pentacarbonyl bearing an OR ligand (R = alkyl, aryl, or silyl) stable enough to be characterized, and it represents also the first molecular model of the surface [Re(CO)5OSi≡] species formed by reductive carbonylation of silica-supported [Re(CO)3OH]4. At room temperature, 1 loses one carbonyl ligand and dimerizes to afford {Re(CO)4[(μ-O)O12Si8(c-C6H11)7]}2 (2), which has been characterized by X-ray diffraction and is the first reported example of a rhenium tetracarbonyl μ-oxo-bridged dimer of the type [Re(CO)4(μ-OR)]2. Copyright
Associative Substitution Reactions of *Re(CO)5
Fox, Arnold,Malito, John,Poe, Anthony
, p. 1052 - 1053 (1981)
Studies of competition between substitution and chlorine abstraction reactions of photochemically generated *Re(CO)5 radicals show that substitution proceeds via a second-order associative path and not via CO dissociation.
Surface organometallic chemistry: Easy reductive carbonylation of silica-supported [Re(CO)3(OH)]4 to [Re2(CO)10] via silica-anchored [Re(CO)5(OSi≡)] and the thermal behavior of silica-supported [Re2(CO)10]
D'Alfonso, Giuseppe,Roberto, Dominique,Ugo, Renato,Bianchi, Claudia L.,Sironi, Angelo
, p. 2564 - 2572 (2000)
Silica-supported [Re(CO)3(OH)]4 is easily converted to [Re2(CO)10] by reductive carbonylation under very mild conditions (1 atm CO). This reaction does not occur in solution, suggesting that the silica surface plays a unique role via the surface-anchored species [Re-(CO)5(OSi)].
Reactivity studies on bimetallic μ-malonyl complexes: cleavage and alkylation chemistry of the malonyl ligand
O'Connor, Joseph M.,Uhrhammer, Roger,Chadha, Raj K.,Tsuie, Barbara,Rheingold, Arnold L.
, p. 143 - 156 (1993)
The bimetallic μ-malonyl complexes: 5-C5Me5)(NO)(PPh3)Re1:C3>Re(CO)4(Br)>-Li+ (1), 5-C5Me5)(NO)(PPh3)Re1:C3>Re(CO)4(PMe3)> * Li+OSO2CF3- (2), and (η5-C5Me5)(NO)(PPh3)Re1,O3:C3>Re(CO)4 (3) undergo carbon-carbon bond cleavage reactions of the malonyl ligand upon exposure to HCl.Deprotonation of (η5-C5Me5)Re(NO)(PPh3)(μ-η1,η2-COCH2CO)Re(CO)4 (3), in THF solution and addition of CH3I leads to the C-alkylation product, (η5-C5Me5)Re(NO)(PPh3)1,O3:C3>Re(CO)4(11), isolated as a single diastereomer (85percent yield).Deprotonation of 11 and alkylation with CD3I leads to (η5-C5Me5)Re(NO)(PPh3)1,O3:C3>Re(CO)4 (12-d3) with > 97percent diastereoselectivity.Alkylation of the enolate anion derived from deprotonation of 11 with ethyl iodide led to isolation of (η5-C5Me5)(NO)(PPh3)Re-C1,O3:C3>Re(CO)4 (21) in 84percent yield.Quenching of the enolate anion of 3 with excess ethyl iodide led to formation of a 11:89 mixture of (η5-C5Me5)(NO)(PPh3)Re1:C3,O3>Re(CO)4 (15) and (η5-C5Me5)(NO)PPh3)Re1,O3:C3>Re(CO)4 (16) in 87percent combined yield.When the enolate anion of 3 was treated with allyl bromide, both C ad O alkylation products (η5-C5Me5)(NO)(PPh3)Re-C1:C3,O1>Re(CO)4 (17) and (η5-C5Me5)(NO)(PPh3)Re-C1,O3:C3>Re(CO)4 (18) were formed in a 32:68 ratio (84percent combined yield).Alkylation with benzyl bromide gave (η5-C5Me5)(NO)(PPh3)Re1,O3:C3>Re(CO)4 (19) in 76percent yield.
Multi-step and multi-component organometallic synthesis in one pot using orthogonal mechanochemical reactions
Hernandez, Jose G.,Butler, Ian S.,Friscic, Tomislav
, p. 3576 - 3582 (2014)
We demonstrate that the mechanochemical strategies for oxidative addition and ligand substitution on organometallic centers can be mutually orthogonal, permitting the rational design of multi-component mechanochemical reaction procedures for assembling complex or solution-sensitive organometallic species from three, four or even five components in one pot. The herein established synthetic procedures represent a new level of complexity in mechanochemical reactions by milling and are the first to combine redox and ligand substitution reactions into mechanochemical strategies for either one-pot sequential ( telescoping ) or one-pot multi-component syntheses. This ability to combine mechanochemical transformations has enabled the solvent-free, room-temperature syntheses of relatively complex organometallics directly for simple zerovalent metal carbonyls as the simplest precursors. In particular, we demonstrate the efficiency of mechanochemical oxidative addition by targeting selected pentacarbonyl halides (fluoride, chloride, bromide, iodide) of rhenium(i) and manganese(i), and illustrate the potential of multi-step organometallic mechanochemistry in the syntheses of selected fac-tricarbonyl complexes of these metals.
[Re(CO)3(bipy)(ClO4)]: Synthesis in a Proton-Donor Solvent, Crystal, and Molecular Structure
Miroslavov,Sidorenko,Tyupina, M. Yu.,Gurzhiy
, p. 2333 - 2337 (2021/02/12)
Abstract: The complex [Re(CO)3(bipy)(ClO4)] (bipy = 2,2?-bipyridine) was prepared by the reaction of [Re(CO)3(H2O,EtOH)3](ClO4) with bipy in aqueous ethanol, followed by crystallization from dichloromethane. The composition and structure of the complex were determined by single crystal X-ray diffraction analysis. The complex has a molecular octahedral structure with bidentate coordination of bipy and inner-sphere monodentate coordination of perchlorate ion in the fac-position to bipy. The complex was also characterized by IR and UV-visible absorption spectroscopy.
