Geometrically Controlled Selective Formation of Nitrido Technetium(V) Asymmetrical Heterocomplexes with Bidentate Ligands

Bolzati, Cristina; Boschi, Alessandra; Duatti, Adriano; Prakash, and Sushumna; Uccelli, Licia; and, Fiorenzo Refosco; Tisato, Francesco; Bandoli, Giuliano

doi:10.1021/ja993834u

Cited by 57 publications

(48 citation statements)

References 10 publications

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“…Succinic dihydrazide was the nitrido source and SnCl 2 the reducing agent. [28][29][30] It should be noted at this point that the synthesis of nitrido complexes in the presence of b-type ligands always lead to Tc V and not to Tc VI compounds. [31] In a subsequent step the two chloride ligands were substituted by a biomolecule pendent ligand (a cysteine for instance), which led to the irreversible labelling of the targeting molecule.…”

Section: Hydrated Coordination Compoundsmentioning

confidence: 99%

The Chemistry of Technetium–Water Complexes within the Manganese Triad: Challenges and Perspectives

Alberto

2008

Eur J Inorg Chem

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The chemistry of technetium is essentially driven by radiopharmaceutical applications. These comprise the syntheses of novel complexes but, moreover, the combination of targeting biomolecules with metal complexes. Aqua ions are especially convenient for facilitatating the introduction of metal cations into biomolecules, but are nonexistent for Tc and Re in the Mn triad. This microreview will discuss the chemistry of those Tc complexes that contain H2O as ligands. Special attention will be payed to organometallic aqua ions, i.e. complexes that are typically organometallic with water as ligand. Of particular interest is the coordination chemistry of [M(OH2)3(CO)3]+ (M = Mn, Tc, Re) complexes in water since it is the origin of the widely applied radiopharmaceutical research with 99mTc and 188Re. The chemistry of organometallic aqua ions is not confined to Werner‐type ligands, hence, a further emphasis will be placed on pure organometallic chemistry in water.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Section: Hydrated Coordination Compoundsmentioning

confidence: 99%

The Chemistry of Technetium–Water Complexes within the Manganese Triad: Challenges and Perspectives

Alberto

2008

Eur J Inorg Chem

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“…An ORTEP view of complex 1 with essential atom numbering. Hydrogen atoms have been omitted for clarity; displacement ellipsoids have been drawn at the 40% probability level Crystalline 1 is made up of well-separated mono-cationic units and PF 6 Ϫ anions, which do not show any interaction below the sum of the van der Waals radii. The environment around the Re atom is square pyramidal, or pseudo-octahedral if we consider the additional weak interaction of N(2) with the metal, with the base plane defined by the P(1), S(1), S(2) and P(2) atoms ( Figure 4).…”

Section: Characterization Of the Complexesmentioning

confidence: 99%

“…Examples of this specific class include the low-valent aqua-carbonyl [Tc I (CO) 3 (OH 2 ) 3 ] ϩ complex [4,5] and high-valent, nitrido-diphosphane [Tc(N)(PNP)Cl 2 ] complexes. [6,7] In these complexes, the [Tc(CO) 3 ] ϩ and [Tc(N)(PNP)] 2ϩ fragments are the stable molecular units. In contrast, the water and halide ϩ FULL PAPER ligands can be efficiently substituted by a series of bi-functional tridentate σ-donor ligands (L) and bidentate π-donor ligands (LЈ), respectively, to yield mixed heterocomplexes of the type [Tc(CO) 3 …”

Section: Introductionmentioning

confidence: 99%

Synthesis, Solution‐State and Solid‐State Structural Characterization of Monocationic Nitrido Heterocomplexes [M(N)(DTC)(PNP)]⁺ (M = ⁹⁹Tc, Re; DTC = Dithiocarbamate; PNP = Heterodiphosphane)

et al. 2004

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Keywords: Technetium / Rhenium / Radiopharmaceuticals / NMR spectroscopy / P ligands (1) displays a distorted, square-pyramidal geometry with the dithiocarbamate sulfur and the diphosphane phosphorus atoms spanning the four coordination positions on the equatorial plane. If the additional interactions between the nitrido nitrogen and the weakly bonded trans N-diphosphane heteroatom, the molecular geometry can be viewed as pseudooctahedral. The structure in solution, as established by multinuclear NMR spectroscopy and ESI spectrometry, is mono-

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“…Hence, the preliminary reaction of a labile nitrido precursor such as [Tc(N)Cl 2 (PPh 3 ) 2 ] with appropriate diphosphine ligands was investigated (Bolzati et al, 2000). It has to be pointed out that diphosphines incorporating merely methylene groups in the spacer invariably produced oily mixtures from which the isolation of pure compounds was unsuccessful.…”

Section: A Chemistry Underlying the Synthesis Of Nitrido Heterocomplmentioning

confidence: 99%

Contribution of electrospray mass spectrometry for the characterization, design, and development of nitrido technetium and rhenium heterocomplexes as potential radiopharmaceuticals

Tisato

Bolzati

Porchia

et al. 2004

Mass Spectrometry Reviews

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Diagnostic nuclear medicine (NM) is among the imaging procedures (together with X-ray, computerized tomography, magnetic resonance, and echography) the clinicians can routinely adopt to image organs or tissues and related disorders. (99m)Tc-based agents are the radiopharmaceuticals of election in diagnostic NM because of the ideal physical properties of the 99mTc nuclide (t1/2 6.01 hr; Egamma 142 keV), low cost, and easy availability through the commercial 99Mo/99mTc generator, and chemical versatility of the element. In the last two decades the synergistic work of clinics, pharmacologists, and coordination chemists has had a tremendous impact in the development of new 99mTc-based radiopharmaceuticals through the recognition of the structure at the molecular level of the agent utilized. This has been achieved by studying the physico-chemical properties of the long-lived 99gTc (t1/2 2.11 x 10(5) year; Ebeta 292 keV) and third-row congener Re isostructural compounds. Electrospray ionization mass spectrometry (ESI-MS) and collision experiments (MS/MS) represent valuable analytical techniques suitable for the characterization of both technetium and rhenium complexes relevant to NM. Unequivocal structural identification of these bioinorganic compounds, either simple coordination complexes ("essential radiopharmaceuticals") or more sophisticated structures carrying bioactive fragments ("receptor-specific" radiopharmaceuticals), can be realized in combination with multinuclear NMR spectroscopy. MS/MS experiments provide useful information on the different metal-ligand bond strength, and comparison of the fragmentation profiles of isostructural technetium and rhenium compounds give additional details on the role played by the metal in determining preferred decomposition channels. The analysis of these data contribute to design novel synthetic strategies for the obtainment of technetium and rhenium compounds relevant to NM. The chemistry underlying the production of a new class of potential radiopharmaceuticals including a terminal nitrogen bond and a mixed coordination sphere comprising heterodiphosphines and/or dithiocarbamates (DTC) is presented in detail together with the ESI-MS and MS/MS investigations.

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Geometrically Controlled Selective Formation of Nitrido Technetium(V) Asymmetrical Heterocomplexes with Bidentate Ligands

Cited by 57 publications

References 10 publications

The Chemistry of Technetium–Water Complexes within the Manganese Triad: Challenges and Perspectives

The Chemistry of Technetium–Water Complexes within the Manganese Triad: Challenges and Perspectives

Synthesis, Solution‐State and Solid‐State Structural Characterization of Monocationic Nitrido Heterocomplexes [M(N)(DTC)(PNP)]⁺ (M = ⁹⁹Tc, Re; DTC = Dithiocarbamate; PNP = Heterodiphosphane)

Contribution of electrospray mass spectrometry for the characterization, design, and development of nitrido technetium and rhenium heterocomplexes as potential radiopharmaceuticals

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Geometrically Controlled Selective Formation of Nitrido Technetium(V) Asymmetrical Heterocomplexes with Bidentate Ligands

Cited by 57 publications

References 10 publications

The Chemistry of Technetium–Water Complexes within the Manganese Triad: Challenges and Perspectives

The Chemistry of Technetium–Water Complexes within the Manganese Triad: Challenges and Perspectives

Synthesis, Solution‐State and Solid‐State Structural Characterization of Monocationic Nitrido Heterocomplexes [M(N)(DTC)(PNP)]+ (M = 99Tc, Re; DTC = Dithiocarbamate; PNP = Heterodiphosphane)

Contribution of electrospray mass spectrometry for the characterization, design, and development of nitrido technetium and rhenium heterocomplexes as potential radiopharmaceuticals

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Synthesis, Solution‐State and Solid‐State Structural Characterization of Monocationic Nitrido Heterocomplexes [M(N)(DTC)(PNP)]⁺ (M = ⁹⁹Tc, Re; DTC = Dithiocarbamate; PNP = Heterodiphosphane)