Synthesis of pyridyl derivatives for the future functionalization of biomolecules labeled with the fac-[<Superscript>188</Superscript>Re(CO)<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>]<Superscript>+</Superscript> precursor

In this paper, we investigated three ligand systems, symmetric and asymmetric pyridyl-containing tridentate ligands (L¹NH₂ = (bis(2-pyridylmethyl)-amino)-ethylamine, L²H = (bis(2-pyridylmethyl)-amino)-acetic acid, L³NH₂ = [(6-amino-hexyl)-pyridyl-2-methyl-amino]-acetic acid) as bifunctional chelating agents for labeling biomolecules. These ligands reacted with the precursor fac-[¹⁸⁸Re(CO)₃(H₂O)₃]⁺ and yielded the radioactive complexes fac-[¹⁸⁸Re(CO)₃L] (L = three ligands), which were identified by RP-HPLC. The corresponding stable rhenium tricarbonyl complexes (1–3) were allowed for macroscopic identification of the radiochemical compounds. ¹⁸⁸Re tricarbonyl complexes, with log P _o/w values ranging from −1.36 to −0.32, were obtained with yields of ≥90% using ligand concentrations within the 10⁻⁶−10⁻⁴M range. Challenge studies with cysteine and histidine revealed the high stability properties of these radioactive complexes, and biodistribution studies in normal mice indicated a fast rate of blood clearance and high rate of total radioactivity excretion, primarily through the renal-urinary pathway. In summary, these asymmetric and symmetric pyridyl-containing tridentate ligands are potent bifunctional chelators for the future biomolecules labeling of fac-[¹⁸⁸Re(CO)₃(H₂O)₃]⁺.     

Synthesis, in vitro and in vivo behavior of 188Re(I)-tricarbonyl complexes for the future functionalization of biomolecules

Radiolabeling of biologically active molecules with fac-[¹⁸⁸Re(CO)₃(H₂O)₃]⁺ unit has been of primary interest in recent years. Therefore, we herein report ligands L¹−L⁴ (L¹=histidine, L²=nitrilotriacetic acid, L³=2-picolylamine-N,N-diacetic acid, L⁴=bis(2-pyridymethy)amine) that have been evaluated by radiochemical reactions with fac-[¹⁸⁸Re(CO)₃(H₂O)₃]⁺. These reactions yielded the radioactive complexes of fac-[¹⁸⁸Re(CO)₃L] (L = L¹−L⁴, ¹⁸⁸Re tricarbonyl complexes 1–4), which were identified by HPLC. Complexes 1–4, with log P _o/w values ranging from −2.23 to 2.18, were obtained with yields of ≥95% using ligand concentrations within 10⁻⁶–10⁻⁴M range. Thus, specific activities of 220 GBq/μmol could be achieved. Challenge studies with cysteine and histidine revealed high stability for all of these radioactive complexes, and biodistribution studies in mice indicated a fast rate of blood clearance and high rate of total radioactivity excretion occurring primarily through the renal-urinary pathway. In summary, the ligands L¹–L⁴ are potent chelators for the future functionalization of biomolecules labeling with fac-[¹⁸⁸Re(CO)₃(H₂O)₃]⁺.     

Characterization and application of the fac-[188Re(CO)3(H2O)3]+ core

Summary Fac-[¹⁸⁸Re(CO)₃(H₂O)₃]⁺ was synthesized with an overall radiochemical yield of 80±5%, and more than 95% radiochemical purity after a QMA Sep-Pak column separation. Fac-[Re(CO)₃(H₂O)₃]⁺ was also synthesized as a reference sample. The structure of the precursor, fac-[¹⁸⁸Re(CO)₃(H₂O)₃]⁺, was confirmed by high performance of liquid chromatography (HPLC). MN-His (magnetic nanoparticles coated with silica and modified with an amino silane coupling agent, N-[3-(trimethyoxysilyl)propyl]-ethylenediamine (SG-Si900) and immobilized with histidine) was labeled with fac-[¹⁸⁸Re(CO)₃(H₂O)₃]⁺ and an initial animal test of MN-His was conducted for a magnetic targeting study.     

Reaction of Sulfur and Oxygen-Bridged 8-Quinolinolato Trinuclear Molybdenum Cluster [Mo<Subscript>3</Subscript>OS<Subscript>3</Subscript>(qn)<Subscript>3</Subscript>(H<Subscript>2</Subscript>O)<Subscript>3</Subscript>]<Superscript>+</Superscript> with Acetylene Carboxylic Acids

The reaction of a sulfur and oxygen-bridged 8-quinolinolato trinuclear molybdenum cluster [Mo₃OS₃(qn)₃(H₂O)₃]⁺ (3; Hqn = 8-quinolinol) with equimolar amounts of acetylene carboxylic acid, 4-pentynoic acid, 5-hexynoic acid, acetic acid, and pimelic acid gave clusters having μ-carboxylato groups, [Mo₃OS₃(qn)₃(H₂O)(μ-HC≡CCOO)] (6), [Mo₃OS₃(qn)₃(H₂O)(μ-HC≡C(CH₂)₂COO)] (7), [Mo₃OS₃(qn)₃(H₂O)(μ-HC≡C(CH₂)₃COO)] (8), [Mo₃OS₃(qn)₃(H₂O)(μ-CH₃COO)] (4), and [{Mo₃OS₃(qn)₃(C₂H₅OH)}₂(μ-C₇H₁₀O₄)] (5), respectively. X-ray structural analyses, ¹H NMR, and electronic spectra of these clusters made clear that each of the COO⁻ groups of the reagents bridges two Mo atoms in each cluster and that no adduct formation occurred at the sulfurs in the clusters. The reaction of 3 with a large excess-molar amount (50 times) of acetylene carboxylic acid gave [Mo₃OS(μ₃-SCH=C(COOH)S)(qn)₃(H₂O)(μ-HC≡CCOO)] (9) with two molecules of acetylene carboxylic acid, one acting as a carboxylato bridge and the other in adduct formation, as supported by the electronic and ¹H NMR spectra. The corresponding aqua cluster [Mo₃OS₃(H₂O)₉]⁴⁺ (1), on the contrary, reacts with acetylene carboxylic acid to give adduct [Mo₃OS(μ₃-SCH=C(COOH)S)(H₂O)₉]⁴⁺ (2). Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Reactivity of triangular oxalate cluster complexes [M<Subscript>3</Subscript>Q<Subscript>7</Subscript>(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>3</Subscript>]<Superscript>2−</Superscript> (M = Mo or W; Q = S or Se)

The reactions of the oxalate complexes [M₃Q₇(C₂O₄)₃]²⁻ (M = Mo or W; Q = S or Se) with Mn^II, Co^II, Ni^II, and Cu^II aqua and ethylenediamine complexes in aqueous and aqueous ethanolic solutions were studied. The previously unknown heterometallic complexes [Mo₃Se₇(C₂O₄)₃Ni(H₂O)₅]·3.5H₂O (1) and K₃{[Cu(en)₂H₂O]([Mo₃S₇(ox)₃]₂Br)}·5.5H₂O (2) were synthesized. In these complexes, the oxalate clusters serve as monodentate ligands. The K(H₂en)₂[W₃S₇(C₂O₄)₃]₂Br·4H₂O salt (3) was isolated from solutions containing Co^II, Ni^II, or Cu^II aqua complexes and ethylenediamine. The reaction of [Mo₃Se₇(C₂O₄)₃]²⁻ with HBr produced the bromide complex [Mo₃Se₇Br₆]²⁻, which was isolated as (Bu₄N)₂[Mo₃Se₇Br₆] (4). Complexes 1–3 were characterized by X-ray diffraction, IR spectra, and elemental analysis. The formation of 4 was detected by electrospray mass spectrometry. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1645–1649, September, 2007.     

Synthesis and biodistribution of the <Superscript>99m</Superscript>Tc(CO)<Subscript>3</Subscript>-DEDT complex as a potential new radiopharmaceutical for brain imaging

The ^99mTc(CO)₃(H₂O)-DEDT complex was prepared by a two-step procedure involving the preparation of the precursor fac-[^99mTc(CO)₃(H₂O)₃]⁺, followed by the addition of sodium salt of diethyl dithiocarbamate (DEDT). The radiochemical purity (RCP) of the product was over 90% as measured by thin layer chromatography (TLC). No decomposition of the complex at room temperature was observed over a period of 6 hours. Its partition coefficient indicated that it was a lipophilic complex. The electrophoresis results showed the complex was neutral. Biodistribution in mice demonstrated that the complex can penetrate the intact blood-brain barrier (BBB) and the brain uptake (ID%/g) was 4.22 at 5-minute post-injection, suggesting the complex may lead to a further development of the radiopharma ceutical as a brain perfusion tracer.     

Preparation and preliminary evaluation of a tris-metronidazole-<Superscript>99m</Superscript>Tc(CO)<Subscript>3</Subscript> complex for targeting tumor hypoxia

Conventional ^99mTc-radiopharmaceuticals for the detection of tumor hypoxia generally possess a single nitroimidazole moiety. Herein, we report the synthesis and evaluation of a ^99mTc-complex with three-nitroimidazole moieties in an attempt to improve hypoxic cell detection. Isocyanide derivative of metronidazole (MetroNC) was synthesized and subsequently radiolabeled with [^99mTc(CO)₃(H₂O)₃]⁺ precursor complex, wherein the three labile water molecules were replaced with MetroNC ligand to form a pseudo-octahedral [^99mTc(CO)₃(MetroNC)₃]⁺ complex. Analysis of corresponding Re(CO)₃-analog prepared in macroscopic scale confirmed the formation of expected complex. Cyclic voltammetric studies of [Re(CO)₃(MetroNC)₃]⁺ complex showed no significant change in single-electron reduction potential (SERP) of MetroNC ligand (??0.96 V) upon forming the [Re(CO)₃(MetroNC)₃]⁺ complex (??0.90 V). In vitro studies in Chinese hamster ovary (CHO) cells showed three-fold preferential accumulation of [^99mTc(CO)₃(MetroNC)₃]⁺ complex in hypoxic cells over normoxic cells. Biodistribution studies of [^99mTc(CO)₃(MetroNC)₃]⁺ complex in Swiss mice bearing fibrosarcoma tumor showed tumor uptake and steady retention till 60 min post injection. Present study constitutes a novel design approach towards development of a ^99mTc-radiopharmaceutical for hypoxia imaging application, which could be extended to other potential nitroimidazole ligands.     

The Reactions of Two New Alkoxy-silyl Functionalized Alkynes with M<Subscript>3</Subscript>(CO)<Subscript>12</Subscript> {M = Fe,Ru} and Co<Subscript>2</Subscript>(CO)<Subscript>8</Subscript>. Spectroscopic Identification of the Products

The new alkoxysilyl-functionalized alkynes [HC≡CCH₂N(H)C(=O)N(H)(CH₂)₃Si(OEt)₃] and [HC≡C(C₆H₄)–N(H)C(=O)N(H)(CH₂)₃Si(OEt)₃] have been synthesized using literature methods. These have been reacted with Fe₃(CO)₁₂, Ru₃(CO)₁₂ and Co₂(CO)₈. With the iron carbonyl only decomposition was observed: with Ru₃(CO)₁₂ splitting of the alkynes into their parent components and formation of the complexes (μ-H)Ru₃(CO)₉[HC=N(CH₂)₃Si(OEt)₃], (μ-H)Ru₃(CO)₉[C–C(C₆H₄)NH₂] and (μ-H)₂Ru₃(CO)₉[HC–CCH₃] occurred. Finally, with Co₂(CO)₈ formation of complexes Co₂(CO)₆(HC₂R) R=(C₆H₄)NH₂, CH₂NH(CO)NH(CH₂)₃Si(OEt)₃, (C₆H₄)NH(CO)NH(CH₂)₃Si(OEt)₃ containing the intact alkynes could be obtained.     

Cuboidal oxalate cluster complexes with the Mo<Subscript>3</Subscript>CuQ<Subscript>4</Subscript><Superscript>5+</Superscript> cluster core (Q = S or Se): synthesis,structure, and electrochemical properties

The reactions of the [Mo₃(μ₃-Q)(μ₂-Q)₃(H₂O)₃(C₂O₄)₃]²⁻ complex (Q = S or Se) with CuX salts (X = Cl, Br, I, or SCN) in water produce the cuboidal heterometallic clusters [Mo₃(CuX)(μ₃-Q)₄(H₂O)₃(C₂O₄)₃]²⁻, which were isolated as the potassium and tetraphenylphosphonium salts. Two new compounds, K₂[Mo₃(CuI)(μ₃-S)₄(H₂O)₃(C₂O₄)₃]·6H₂O and (PPh₄)₂[Mo₃(CuBr)(μ₃-S)₄(H₂O)₃(C₂O₄)₃]·7H₂O, were structurally characterized. All compounds were characterized by elemental analysis and IR spectroscopy. The K₂[Mo₃(CuI)(μ₃-Se)₄(H₂O)₃(C₂O₄)₃] compound was characterized by the ⁷⁷Se NMR spectrum; the (PPh₄)₂[Mo₃(CuI)(μ₃-S)₄(H₂O)₃(C₂O₄)₃], (PPh₄)₂[Mo₃(CuI)(μ₃-Se)₄(H₂O)₃(C₂O₄)₃] and K₂[Mo₃(CuSCN)(μ₃-S)₄(H₂O)₃(C₂O₄)₃]·7H₂O compounds, by electrospray mass spectra. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1639–1644, September, 2007.     

Reactions of [Cp*Ru(H<Subscript>2</Subscript>O)(NBD)]<Superscript>+</Superscript> with diynes

Abstract  Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H₂O)(NBD)][BF₄] (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BF₄]₂. The reaction of [Cp*Ru(H₂O)(NBD)][BF₄] with 1,4-diphenylbutadiyne generates the unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C₉H₈–Ph in addition to the organometallic compound [Cp*Ru(η⁶-C₆H₅–C≡C–C≡C–Ph)][BF₄]. [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BPh₄]₂ is generated after the reaction of compound [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BF₄]₂ with Na[BPh₄]. The structure of this compound was confirmed by X-ray diffraction. A possible approach to form Ph–C≡C–C₉H₈–Ph and [Cp*Ru(η⁶-C₆H₅–C≡C–C≡C–Ph)][BF₄] is suggested. Graphical Abstract  Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H₂O)(NBD)]BF₄ (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BF₄]₂. The reaction of [Cp*Ru(H₂O)(NBD)][BF₄] with 1,4-diphenylbutadiyne simply generates unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C₉H₈–Ph in addition to the organometallic compound [Cp*Ru(η⁶-C₆H₅–C≡C–C≡C–Ph)][BF₄]. [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BPh₄]₂ is generated after the reaction of compound [C₉H₉-η⁶-C₆H₄(RuCp*)–C₆H₄(RuCp*)-η⁶-C₉H₉][BF₄]₂ with Na[BPh₄]. The structure of this compound was confirmed by X-ray diffraction. And the possible approach to form Ph–C≡C–C₉H₈–Ph and [Cp*Ru(η⁶-C₆H₅–C≡C–C≡C–Ph)][BF₄] was suggested. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Gas phase structure of micro-hydrated [Mn(ClO<Subscript>4</Subscript>)]<Superscript>+</Superscript> and [Mn<Subscript>2</Subscript>(ClO<Subscript>4</Subscript>)<Subscript>3</Subscript>]<Superscript>+</Superscript> ions probed by infrared spectroscopy

Gas-phase infrared photodissociation spectroscopy is reported for the microsolvated [Mn(ClO₄)(H₂O) _n ]⁺ and [Mn₂(ClO₄)₃(H₂O) _n ]⁺ complexes from n = 2 to 5. Electrosprayed ions are isolated in an ion-trap where they are photodissociated. The 2600–3800 cm⁻¹ spectral region associated with the OH stretching mode is scanned with a relatively low-power infrared table-top laser, which is used in combination with a CO₂ laser to enhance the photofragmentation yield of these strongly bound ions. Hydrogen bonding is evidenced by a relatively broad band red-shifted from the free OH region. Band assignment based on quantum chemical calculations suggest that there is formation of water—perchlorate hydrogen bond within the first coordination shell of high-spin Mn(II). Although the observed spectral features are also compatible with the formation of structures with double-acceptor water in the second shell, these structures are found relatively high in energy compared with structures with all water directly bound to manganese. Using the highly intense IR beam of the free electron laser CLIO in the 800–1700 cm⁻¹, we were also able to characterize the coordination mode (η²) of perchlorate for two clusters. The comparison of experimental and calculated spectra suggests that the perchlorate Cl—O stretches are unexpectedly underestimated at the B3LYP level, while they are correctly described at the MP2 level allowing for spectral assignment.     

Formation of 1-D polymer in recrystallization of the adduct Mn[(OOCC<Subscript>5</Subscript>H<Subscript>4</Subscript>)Mn(CO)<Subscript>3</Subscript>]<Subscript>2</Subscript>[O(H)Me]<Subscript>4</Subscript> from acetonitrile

It was found that the recrystallization of the adduct Mn[(OOCC₅H₄)Mn(CO)₃]₂[O(H)Me]₄ from hot acetonitrile in the presence of benzene produces polymer [μ-(OOCC₅H₄)Mn(CO)₃]₄[μ-η²-(OOCC₅H₄)Mn(CO)₃]₂(NCMe)₂(OH₂)₂([μ-η²-(OOCC₅H₄)Mn(CO)₃]₂)[μ-(OOCC₅H₄)Mn(CO)₃]₄[μ-η²-(OOCC₅H₄)Mn(CO)₃]₂(OH₂)_2n. The obtained polymer was characterized by X-ray diffraction analysis.     

Deoxygenation of Nitrosobenzene by the Electrogenerated Pd<Subscript>3</Subscript>(dppm)<Subscript>3</Subscript>(μ<Subscript>3</Subscript>-CO) Cluster

The 2-electron reduction of the unsaturated Pd₃(dppm)₃(CO)²⁺ cluster ([Pd₃]²⁺) affords the highly reactive neutral cluster [Pd₃]⁰, which reacts with nitrosobenzene (PhNO) yielding the organic azoxybenzene product (PhN(O)NPh) via the formation of “triplet” nitrene “PhN”. The formation of [Pd₃(μ₃-O)] as a possible (relatively unstable) intermediate is also postulated based on MALDI-TOF findings, but not formally demonstrated. Concurrently, no reaction between [Pd₃]⁰ and OPPh₃ occurs. Electronic supplementary material The online version of this article (doi: ) contains supplementary material, which is available to authorized users. This paper is dedicated to Professor Dieter Fenske.     

S-bridged complex of <Superscript>99m</Superscript>Tc with <Emphasis Type="Italic">fac</Emphasis>(S)-[Rh(aet)<Subscript>3</Subscript>]: Quality control,characterization and biodistribution studies in rats

fac(S)-[Rh(aet)₃] (aet = 2-aminoethanethiolate) is N₃S₃ metalloligand which can coordinate to transition metal ions to form S-bridge polynuclear complexes. The reaction was carried out between ^99mTcO₄Na and fac(S)-[Rh(aet)₃] in the presence of SnCl₂·2H₂O. A complex analogous to [Re{Rh(aet₃)}₂]³⁺ is formed.⁶ A simple method for radiolabeling of fac(S)-[Rh(aet)₃] with ^99mTc has been developed and radiolabeling efficiency was higher than 99%. Effect of SnCl₂·2H₂O concentration, electrophoresis, HPLC, UV-Visible absorption spectra and biodistribution studies in rats were performed. Higher uptake by kidneys showed rapid distributions of the labeled fac(S)-[Rh(aet)₃]. Liver uptake was significant, stomach, lungs and intestine uptake was high at 4 hours post injection time.     

Complexes based on the anionic octahedral rhenium chalcogenide clusters and [M(En)<Subscript>2</Subscript>]<Superscript>2+</Superscript> (M = Ni,Cu) cations

The compounds [Ni(H₂O)₂(En)₂][{Ni(En)₂}Re₆S₈(OH)₆] · 7H₂O (I), [{Cu(En)₂}Re₆S₈(H₂O)₂(OH)₄] · 4H₂O (II), and [Ni(H₂O)₂(En)₂]_0.5[Re₆Se₈(H₂O)₃(OH)₃] · 10H₂O (III) were synthesized by layering aqueous solutions of Ni(En)₂Cl₂ or Cu(En)₂Cl₂ (En is ethylenediamine) onto aqueous solutions of the potassium salts of the corresponding octahedral chalcohydroxo rhenium cluster complexes [Re₆Q₈(OH)₆]⁴⁻ (Q = S, Se). The structure of the obtained compounds was determined by X-ray diffraction analysis.     

Hydrothermal synthesis and crystal structure of [Ni(Bptc)<Subscript>2</Subscript>(Bimb)<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>]

In the compound [Ni(Bptc)₂(Bimb)₂(H₂O)₂] (I), where H₄Bptc is 3,3′,4,4′-biphenyltetracarboxylic acid; Bimb is 4,4′-bis(1-imidazolyl)biphenyl), Ni(II) has a distorted octahedral coordination geometry, which was bonded with two N atoms from two Bimb ligands, two O atoms from two H₂Bptc²⁻ ligands and two water O atoms. The crystal structure of compound I is stabilized by the π-π-stacking and hydrogen bonds interaction.     

Capping [H<Subscript>8−n</Subscript>Ni<Subscript>42</Subscript>C<Subscript>8</Subscript>(CO)<Subscript>44</Subscript>]<Superscript>n−</Superscript> (n = 6, 7, 8) Octa-carbide Carbonyl Nanoclusters with [Ni(CO)] and [CuCl] Fragments

The reactions of [Ni₁₆(C₂)₂(CO)₂₃]^4? and [Ni₃₈C₆(CO)₄₂]^6? with CuCl afforded mixtures of the previously reported [HNi₄₂C₈(CO)₄₄(CuCl)]^7? bimetallic octa-carbide cluster and the new [HNi₄₃C₈(CO)₄₅]^7? and [HNi₄₄C₈(CO)₄₆]^7? homo-metallic octa-carbides. The three species have very similar properties resulting always in co-crystals such as [NMe₄]₇[HNi_42+2xC₈(CO)_44+2x(CuCl)_1?x]·6.5MeCN (x = 0.14) (86% [HNi₄₂C₈(CO)₄₄(CuCl)]^7?, 14%[HNi₄₃C₈(CO)₄₅]^7?/[HNi₄₄C₈(CO)₄₆]^7?) and [NMe₄]₇[HNi_42+2xC₈(CO)_44+2x(CuCl)_1?x]·5.5MeCN (x = 0.30) (70% [HNi₄₂C₈(CO)₄₄(CuCl)]^7?, 30% [HNi₄₃C₈(CO)₄₅]^7?/[HNi₄₄C₈(CO)₄₆]^7?). The new homo-metallic octa-carbides can be obtained free from the Ni–Cu octa-carbido cluster by reacting [Ni₁₀(C₂)(CO)₁₆]^2? in thf with a stoichiometric amount of CuCl, and crystals of [NMe₄]₆[H₂Ni_43+xC₈(CO)_45+x]·6MeCN (x = 0.72), which contain [H₂Ni₄₄C₈(CO)₄₆]^6? (72%) and [H₂Ni₄₃C₈(CO)₄₅]^6? (28%), have been obtained. Despite the different charges and compositions, these anions display almost identical structures, which are also closely related to those previously reported for the bimetallic Ni–Cd octa-carbido clusters [Ni_42+xC₈(CO)_44+x(CdCl)]^7? and [HNi_42+xC₈(CO)_44+x(CdBr)]^6?. Indeed, all these clusters are based on the same Ni₄₂C₈ cage decorated by miscellaneous [CdX]⁺ (X = Cl, Br), [CuCl] and [Ni(CO)] fragments.     

Synthesis of a <Superscript>188</Superscript>Re–DTPMP complex using carrier-free <Superscript>188</Superscript>Re and study of its stability

Labeling of diethylenetriamine-N,N,N′,N″,N″-pentakis(methylenephosphonic) acid (DTPMP) with rhenium-188 using stannous chloride as a reducing agent has been investigated. Dependence of the yield of the ¹⁸⁸Re–DTPMP complex on the concentration of the reducing agent, pH, reaction time, temperature, ascorbic acid and amount of carrier added has been studied. Under optimum conditions, the labeling yield of ¹⁸⁸Re–DTPMP complex is 95% for the carrier-free ¹⁸⁸Re but with the carrier-added ¹⁸⁸Re the labeling yield is more than 97%. Furthermore, the stability of the ¹⁸⁸Re–DTPMP complex against pH change and dilution with saline has been also studied. It is found that the addition of carrier stabilizes the ¹⁸⁸Re–DTPMP complex against pH change and dilution.     

A New Molybdophosphate Constructed From {Mo<Stack><Subscript>2</Subscript><Superscript>V</Superscript></Stack>O<Subscript>4</Subscript>(H<Subscript>2</Subscript>O)<Subscript>6</Subscript>}<Superscript>2+</Superscript> and 1-Hydroxyethylidenediphosphonate

A new molybdophosphate (NH₄)₈{Mo₂^VO₄[(Mo₂^VIO₆)CH₃C(O)(PO₃)₂]₂}·14H₂O (1), has been synthesized by the reaction of {Mo₂^VO₄(H₂O)₆}²⁺ fragments with 1-hydroxyethylidenediphosphonate (hedp HOC(CH₃)(PO₃H₂)₂), and it is characterized by ³¹P NMR, IR, UV, element analysis, TG and single-crystal X-ray analysis. The structure analysis reveals that the polyoxoanion can be described as two {(Mo₂^VIO₆)(CH₃C(O)(PO₃)₂} units connected by a {Mo₂^VO₄}²⁺ moiety. In the structure, the six Mo atoms are arranged into a new “W-shaped” structure, which represents a new kind of molybdophosphate.     

Electroneutral coordination frameworks based on octahedral [Re<Subscript>6</Subscript>(μ<Subscript>3</Subscript>-Q)<Subscript>8</Subscript>(CN)<Subscript>6</Subscript>]<Superscript>4−</Superscript> complexes (Q = S,Se, Te) and the Mn<Superscript>2+</Superscript> cations

The novel coordination polymers, [{Mn(DMF)₃}₂{Re₆S₈(CN)₆}] (I), [{Mn(DMF)₂(H₂O)}₂{Re₆S₈(CN)₆}] · 2DMF (II), [{Mn(DMF)₃}₂{Re₆Se₈(CN)₆}] (III), [{Mn(DMF)₂(H₂O)}₂{Re₆Se₈(CN)₆}] · 2DMF (IV), and [{Mn(DMF)₂(H₂O)}₂{Re₆Te₈(CN)₆}] · 2DMF (V), were synthesized by interaction of the octahedral cluster complexes [Re₆(μ₃-Q)₈(CN)₆]^4? (Q = S, Se, Te) with the Mn²⁺ cations in the H₂O-DMF mixture. The crystal structures of compounds I, II, IV, and V were determined by X-ray diffraction analysis. The structural analogies between mononuclear cyanometallates and the obtained cluster coordination polymers were discussed.