Developing the {M(CO)3}+ core for fluorescence applications: Rhenium tricarbonyl core complexes with benzimidazole, quinoline, and tryptophan derivatives

Tridentate ligands derived from benzimidazole, quinoline, and tryptophan have been synthesized, and their reactions with [NEt4]2[Re(CO)3Br3] have been investigated. The complexes 1-4 and 6 and 7 exhibit fac-{Re(CO)3N3} coordination geometry in the cationic molecular units, while 5 exhibits fac-{Re(CO)3N2O} coordination for the neutral molecular unit, where N3 and N2O refer to the ligand donor groups. The ligands bis(1-methyl-1H-benzoimidazol-2-ylmethyl)amine (L1), [bis(1-methyl-1H-benzoimidazol-2-ylmethyl)amino]acetic acid ethyl ester (L2), [bis(1-methyl-1H-benzoimidazol-2-ylmethy)amino]acetic acid methyl ester (L3), [bis(quinolin-2-ylmethyl)amino]acetic acid methyl ester (L4), 3-(1-methyl-1H-indol-3-yl)-2-[(pyridin-2-ylmethyl)amino]propionic acid (L5), 2-[bis(pyridin-2-ylmethyl)amino]-3-(1-methyl-1H-indol-3-yl)propionic acid (L6), and 2-[bis(quinolin-2-ylmethyl)amino]-3-(1-methyl-1H-indol-3-yl)propionic acid (L7) were obtained in good yields and characterized by elemental analysis, 1D and 2D NMR, and high-resolution mass spectrometry (HRMS). The rhenium complexes were obtained in 70-85% yields and characterized by elemental analysis, 1D and 2D NMR, HRMS, IR, UV, and luminescence spectroscopy, as well as X-ray crystallography for [Re(CO)3(L1)]Br (1), {[Re(CO)3(L2)]Br}2.NEt4Br . 8.5H2O (3(2).NEt4Br . 8.5H2O), [Re(CO)3(L4)]Br (4), and [Re(CO)3(L6)]Br (6). Crystal data for C21H19BrN5O3Re (1): monoclinic, P2(1)/c, a = 13.1851(5) A, b = 16.1292(7) A, c = 10.2689(4) A, beta = 99.353(1) degrees , V = 2154.8(2) A3, Z = 4. Crystal data for C56H73Br3N11O18.50 Re2 (3(2).NEt4Br . 8.5H2O): monoclinic, C2/c, a = 34.7760(19) A, b = 21.1711(12) A, c = 20.3376(11) A, beta = 115.944(1) degrees , V = 13464.5(1) A3, Z = 8. Crystal data for C26H21BrN3O5Re (4): monoclinic, P2(1)/c, a = 16.6504(6) A, b = 10.1564(4) A, c = 14.6954(5) A, beta = 96.739(1) degrees , V = 2467.9(2) A3, Z = 4. Crystal data for C27H24BrN4O5Re (6): monoclinic, P2(1), a = 8.7791(9) A, b = 16.312(2) A, c = 8.9231(9) A, beta = 90.030(1) degrees , V = 1277.8(2) A3, Z = 2.     

Binuclear complexes from ω-cyanoalkyl derivatives of cyclopentadienylmanganese tricarbonyl and benzenechromium tricarbonyl

Conclusions The reaction of the-cyanoalkyl derivatives of cyclopentadienylmanganese tricarbonyl and benzenechromium tricarbonyl with chromium and tungsten carbonyls gave binuclear complexes with the same, as well as with different metals in the molecule.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 722–725, March, 1978.     

Rhenium(I) tricarbonyl complexes with bispyridine ligands attached to sulfur-rich core: Syntheses, structures and properties

Rhenium(I) tricarbonyl complexes with bispyridine ligands bearing sulfur-rich pendant, Re(CO)₃(Medpydt)X (Medpydt = dimethyl 2-(di(2-pyridyl)methylene)-1,3-dithiole-4,5-dicarboxylate; X = Cl, 1; X = Br, 2) and Re(CO)₃(MebpyTTF)X (MebpyTTF = 4,5-bis(methyloxycabonyl)-4′,5′-(4′-methyl-2,2′-dipyrid-4-ylethylenedithio)-tetrathiafulvalene; X = Cl, 5; X = Br, 6), were prepared from the reactions between Re(CO)₅X (X = Cl, Br) and Medpydt or MebpyTTF, respectively. Hydrolysis of the above complexes afforded the analogues with carboxylate derivatives, Re(CO)₃(H₂dpydt)X (X = Cl, 3; X = Br, 4) and Re(CO)₃(H₂bpyTTF)X (X = Cl, 7; X = Br, 8). The crystal structures for complexes 1 · 2H₂O, 5 and 6 were determined using X-ray single crystal diffraction. UV-Vis absorption spectra of the rhenium complexes show the intraligand and MLCT transitions. Electrochemical behaviors of all new compounds were studied with cyclic voltammetry. Upon irradiation, complexes 3-6 exhibit blue to red emissions in fluid solutions at the room temperature. The performance of complexes 3, 4, 7 and 8 as photosensitizers for anatase TiO₂ solar cells was preliminarily investigated as well.     

Rhenium(I) tricarbonyl complexes of 5,10,15,20-tetraphenyl-21-thia and 21-oxaporphyrins

The hexa-coordinated rhenium(I) tricarbonyl complexes of 5,10,15,20-tetraphenyl-21-thiaporphyrin 1 and 5,10,15,20-tetraphenyl-21-oxaporphyrin 2 have been synthesized by thermal reaction of corresponding free base porphyrin with Re(2)(CO)(10). The compounds 1 and 2 are characterized by HR-MS mass, (1)H, and (13)C NMR, FTIR, UV-vis, and electrochemical techniques and the structures are determined by X-ray single crystal analysis. The X-ray analysis revealed different coordination behavior of Re(CO)(3) with 21-thiaporphyrin and 21-oxaporphyrin. Interestingly, the Re(CO)(3) coordinates to two of the three inner nitrogens and one sulfur instead of three inner nitrogens as generally expected to produce unique compound 1 whereas it coordinates to three inner nitrogens but not with furan oxygen to form compound 2. The 21-thiaporphyrin ring is more distorted in compound 1 compared to 21-oxaporphyrin ring in compound 2 on complexation with Re(CO)(3). The presence of three carbonyl groups in compounds 1 and 2 are verified by (13)C NMR and IR spectroscopy. The absorption spectra of compounds 1 and 2 showed ill-defined Q-bands along with broad Soret band and the extinction coefficients are much lower than their corresponding free base porphyrins. The compounds 1 and 2 showed two reversible porphyrin ring based reductions supporting their electron deficient nature. The compound 1 is very stable under protonation conditions, and the protonation occurs at the uncoordinated pyrrole ring whereas the compound 2 undergoes decomplexation under same conditions. Furthermore, compound 1 showed the fluxional behavior in coordination mode of binding in solution.     

Rhenium fac tricarbonyl bisimine complexes: biologically useful fluorochromes for cell imaging applications

A series of lipophilic and hydrophilic fac tricarbonyl rhenium bisimine complexes have been prepared, their membrane-permeabilities explored in liposomes and their potential for application in fluorescence microscopy cell imaging demonstrated in the first application of MLCT-fluorescent rhenium complexes in cell imaging.     

Rhenium complexes with triazine derivatives formed from semicarbazones and thiosemicarbazones

Benzil bis(semicarbazone), H2L(1), reacts with common rhenium(V) nitrido complexes such as [ReNCl2(PPh3)2] or [ReNCl2(PR2Ph)3] (R = Me, Et) under the release of one semicarbazone unit, cyclization, and formation of stable triazine-3-onato complexes of rhenium(V). The resulting 5,6-diphenyltriazine-3-one, HL (2), acts as monodentate or chelating, monoanionic ligand depending on the reaction conditions applied. Complexes of the compositions [ReNCl(L(2)-kappaN(2),kappaO)(PR2Ph)2] (R = Me, Et) or [ReN(L(2)-kappa N(2),O)(L(2)-kappaN(2))(PPh3)2] were isolated. The N(2) nitrogen atom is the preferred binding site of the monodentate form of the ligand. This contrasts the behavior of the analogous thione HL(3), which preferably coordinates to nitridorhenium(V) centers via the sulfur atom. HL(3) is readily formed by the abstraction of methanol from 5-methoxy-5,6-diphenyl-4,5-dihydro-2H-[1,2,4]triazine-3-thione, H2L(3)OCH 3. In the presence of [ReNCl2(PPh3)2] or [ReNCl2(PR2Ph)3] complexes (R = Me, Et), this reaction yields stable complexes of the composition [ReN(L(3)-kappaN(2),kappaS)(L(3)-kappaS)(PR2Ph)2] (R = Me, Et, Ph) in good yields. Reduction of the metal atom and formation of the seven-coordinate [Re(PPh3)(L(3)-kappaN(2),kappaS)3] was observed during reactions of H2L(3)OCH3 with [ReOCl3(PPh3)2] or [ReO2I(PPh3)2], while no rhenium complexes could be isolated during similar reactions with H2L(1), although cyclization of the bis(semicarbazone) and the formation of H 2L(2)OEt were observed.     

Protonation of homotroponeiron tricarbonyl and cyclooctatrienoneiron tricarbonyl complexes

2,3-Homotroponeiron tricarbonyl, 8-methyl- and 8,8-dimethyl-2,3-homotroponeiron tricarbonyl complexes have been shown to undergo O-protonation in trifluoroacetic (TFA) and 96% sulfuric acids. In the latter acid the O-protonated cations rearrange to give the thermodynamically more stable C-protonated isomers. Cyclooctatrienoneiron tricarbonyl undergoes protonation H₂SO₄ to give the same cation as was obtained from the protonation of the homotroponeiron tricarbonyl complex in H₂SO₄. On the basis of reaction in D₂SO₄, it is suggested that the kinetically preferred site of protonation of the cyclooctatrienone complex is at C(2) one of the coordinated carbon atoms.     

Rhenium(I)- and technetium(I) tricarbonyl complexes anchored by bifunctional pyrazole-diamine and pyrazole-dithioether chelators

The novel pyrazolyl containing ligands 4-(HOOC)pz(CH₂)₂NH(CH₂)₂NH₂ (L¹) and 4-(HOOCCH₂)-3,5-Me₂pz(CH₂)₂NH(CH₂)₂NH₂ (L²), and 3,5-Me₂pz(CH₂)₂S(CH₂)₂SCH₂CH₃ (L³), 3,5-Me₂pz(CH₂)₂S(CH₂)₂SCH₂COOEt (L⁴) and 3,5-Me₂pz(CH₂)₂S(CH₂)₂SCH₂COOH (L⁵) were synthesized, and their ability to stabilise complexes with the fac-[M(CO)₃]⁺ (M = Re,^99mTc) moiety was evaluated. Reactions of L¹-L⁵ with the Re(I) tricarbonyl starting materials (NEt₄)₂[Re(CO)₃Br₃] and/or [Re(CO)₅Br] afforded complexes fac-[Re(CO)₃(κ³-L)] (L = L¹-L⁵ (1-5)), which contain the pyrazolyl ancillary ligands coordinated in a tridentate fashion. Complexes 1-5 were characterized by the common analytical techniques, which included single crystal X-ray diffraction analysis in the case of 4. The structural analysis of 4 confirmed the tridentate coordination mode of the pyrazole-dithioether ligand, which is facially coordinated to the Re(I) centre through the nitrogen from the pyrazole ring and the two thioether sulphur atoms, without involvement of the terminal ester functional group. The distorted octahedral coordination environment around the metal is completed by the three facial carbonyl ligands. The radioactive congeners of complexes 1, 3 and 4, fac-[^99mTc(CO)₃(κ³-L)]⁺ (L = L¹ (1a), L³ (3a), L⁴ (4a)), have been prepared by reacting the precursor fac-[^99mTc(CO)₃(H₂O)₃]⁺ with the corresponding ligands, and their identity confirmed by HPLC comparison with the rhenium surrogates. Complexes 1a and 3a have been challenged in the presence of a large excess of histidine or cysteine, in order to evaluate their in vitro stability. Only a negligible displacement was observed, indicating that pyrazole-diamine and pyrazole-dithioether chelators provide a high kinetic inertness and/or stability to organometallic complexes with the fac-[^99mTc(CO)₃]⁺ moiety.     

Rhenium and technetium tricarbonyl complexes anchored by pyrazole-based tripods: novel lead structures for the design of myocardial imaging agents

This report describes the synthesis and biological evaluation of cationic (99m)Tc-tricarbonyl complexes anchored by ether-containing tris(pyrazolyl)methane or bis(pyrazolyl)ethanamine ligands to be applied in the design of radiopharmaceuticals for myocardial imaging: fac-[(99m)Tc(CO)(3){RC(pz)(3)}](+) (R = H (1a), MeOCH(2) (2a), EtOCH(2) (3a), (n)PrOCH(2) (4a)) and fac-[(99m)Tc(CO)(3){RNHCH(2)CH(pz)(2)}](+) (R = H (5a), MeO(CH(2))(2) (6a)) (pz = pyrazolyl). At the no carrier added level, complexes 1a-6a were obtained in high radiochemical yield (> 98%) by reaction of fac-[(99m)Tc(CO)(3)(H(2)O)(3)](+) with the corresponding tripod chelator in aqueous medium. All these complexes display a high in vitro and in vivo stability, except 6a which metabolizes in vivo yielding fac-[(99m)Tc(CO)(3){HO(CH(2))(2)NHCH(2)CH(pz)(2)}](+) (7a). Biological studies in mice have shown that among the radiotracers evaluated in this work, 3a, anchored by a tris(pyrazolyl)methane chelator bearing an ethyl methyl ether substituent, has the highest heart uptake (3.6 +/- 0.5%ID g(-1) at 60 min p.i.). Complex 3a presents also the best heart: blood, heart: liver and heart: lung ratios, appearing as the most promising as a potential myocardial imaging agent. The chemical identity of 1a-7a was ascertained by HPLC comparison with the previously reported fac-[Re(CO)(3){HC(pz)(3)}]Br (1) and with the novel fac-[Re(CO)(3){RC(pz)(3)}]Br (R = MeOCH(2) (2), EtOCH(2) (3), (n)PrOCH(2)(4)) and fac-[Re(CO)(3){RNHCH(2)CH(pz)(2)}]Br (R = H (5), MeO(CH(2))(2) (6) HO(CH(2))(2) (7)). The novel Re(I) tricarbonyl complexes, 2-7, were characterized by the common analytical techniques, including single crystal X-ray diffraction analysis. The solid state structure confirmed the presence of facial and tridentate (kappa(3)-N(3)) anchor ligands. Solution NMR studies have also shown that this kappa(3)-N(3) coordination mode is retained in solution for all complexes (2-7).     

Arene derivatives of molybdenum and tungsten Communication 1. Anisole tricarbonyl complexes of molybdenum and tungsten

Conclusions The reaction of anisole with the molybdenum and tungsten hexacarbonyls gave the previously unknown antsole complexes (C₆H₅OCH₃)M(CO)₃.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2090–2091, September, 1973.The authors express their gratitude to P. V. Petrovskii for assistance in taking and discussing the NMR spectra.     

Iron tricarbonyl complexes of hydroxypolymethylbenzolonium ions

Russian Chemical Bulletin -     

Electrochemical reduction of arenechromium tricarbonyl complexes

Conclusions A study was made of the electrochemical reduction of some -ArCr(CO)₃ complexes at a mercury dropping electrode in dimethylformamide on a support of 0.1 NEt₄NClO₄ solution.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 471–473, February, 1975.     

One-step protection of the nucleoside base in thymidine and uridine

Unprotected thymidine and uridine react with 4-nitrophenylsulfonyl ethene ($\text{3}$) in a base catalyzed Michael type addition to give O⁴-(4-nitrophenylsulfonylethyl)thymidine-($\text{6}$) and -uridine ($\text{7}$), respectively. The 4-nitrophenylsulfonylethyl group is cleaved within 2.5 hours at 50–55°C by concentrated aqueous ammonia, via β-elimination.     

(Dihydropyridine)iron tricarbonyl complexes

(N-Carboalkoxy-1,2-dihydropyridine)iron tricarbonyl complexes have been isolated by treatment of either N-carboalkoxy-1,2 or -1,4-dihydropyridines with diiron ennecarbonyl. The organic ligand was liberated from these complexes by use of trimethylamine oxide.     

Dynamics and structure of some tricarbonylferrole-iron tricarbonyl derivatives

A series of compounds of the formula Fe₂(CO)_6-x(PR₃)_x(R′C₂R″)₂ (x = 0, R′ and R″ = Ph, R′ and R″ = H, R′ = Ph and R″ = H; x = 1, K = Ph or n-Bu, and R′ and R″ = Ph) were studied by ¹³C NMR to observe their solution properties. The tricarbonylferrole unit was found to be static from ?125 to +95° C, while the π-Fe(CO)₃ group appeared to be fluxional over the same temperature range. Definite assignments of the carbonyl carbon and ferrole ring carbon resonances have been made. A low temperature single crystal X-ray study of Fe₂(CO)₅PPh₃(PhC₂Ph)₂ demonstrated that the phosphine ligand was attached to the ferrole iron contrary to previous belief based on chemical evidence.