Synthesis, characterization, and x-ray structural determinations of technetium(V)-oxo-tetradentate amine oxime complexes

Jurisson, S.S.; Schlemper, E. O.; Troutner, D.E.; Canning, Lewis R.; Nowotnik, David P.; Neirinckx, R.D.

doi:10.1021/ic00224a031

Cited by 99 publications

(64 citation statements)

References 2 publications

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“…The average Tc-O bond distance of 1.67 Å is consistent with that seen in other TcO(PnAO) structures. 2,3,8 Tc-N (amide and amine) distances and the angles in the chelate rings are also comparable to those seen previously (Table 2). In both of the TcO(PnAO-6-R) compounds structurally characterized here, the six-member chelate ring that includes the propylene bridge adopted a boat conformation.…”

Section: Discussionsupporting

confidence: 89%

See 1 more Smart Citation

Technetium(V) Oxo Complexes of Substituted Propylene Diamine Dioxime (PnAO) Ligands: Water-Dependent Interconversion between Syn and Anti Isomers

Cyr¹,

Nowotnik²,

Pan³

et al. 2001

Inorg. Chem.

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99mTc and (99)Tc complexes of PnAO (propylene diamine dioxime) ligands monosubstituted in the 6-position [PnAO-6-R] were prepared and studied. Ligands substituted with an alkyl group or with no substituent (R = H, CH(3), or CH(2)CH(CH(3))(2)), gave only one Tc complex. However, for several other nonalkyl substituents (R = COOCH(3), OH, OCH(3), OCH(2)CH(3), F, CN, NHCOCH(3), and NHCOCH(2)CH(3)), two Tc complexes A and B were formed. Products A and B were assigned to the anti and syn TcO(PnAO-6-R) species, respectively, based on (1)H NMR results. X-ray structure analyses supported these assignments. The A (anti) isomer of TcO(PnAO-6-OH) had the chemical formula TcC(13)H(25)N(4)O(4) and crystallized in an orthorhombic system with space group P2(1)2(1)2(1) and Z = 4; a = 12.744(2) A, b = 13.591(2) A, c = 9.976(2) A. The B (syn) isomer of TcO(PnAO-6-CN) had the chemical formula TcC(14)H(24)N(5)O(3) and was a 1:4 mixture of two monoclinic polymorphs: individual rectangular prisms (space group P2(1)/c, Z = 4) and clusters of intergrown twinned rectangular rods (space group Cc, Z = 8). For the prisms, a = 12.457(1) A, b = 13.932(1) A, c = 10.336(1) A, and for the rods, a = 31.344(5) A, b = 6.993(1) A, c = 21.657(2) A. The syn and anti isomers interconverted in the presence of water; nonequilibrium mixtures of epimers remained unchanged under dry conditions. The HPLC behavior under reversed phase conditions was consistent with on-column interconversion (poor resolution), whereas the two isomers were cleanly resolved under drier normal phase conditions. An oxo inversion mechanism involving trans water attack is proposed for the interconversion process. Water also influenced the position of equilibrium of the two isomers. The syn isomer was stabilized in water relative to the anti isomer.

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Section: Discussionsupporting

confidence: 89%

“…2,3,8 Both complexes are five-coordinate and have square-pyramidal geometry with the oxo group occupying the apical position. The ligands lose three protons (one oxime and two amine protons) on coordination to technetium, forming a neutral Tc(V) complex with strong intramolecular hydrogen bonding between oxime oxygen atoms.…”

Section: Discussionmentioning

confidence: 99%

Technetium(V) Oxo Complexes of Substituted Propylene Diamine Dioxime (PnAO) Ligands: Water-Dependent Interconversion between Syn and Anti Isomers

Cyr¹,

Nowotnik²,

Pan³

et al. 2001

Inorg. Chem.

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“…13 The two bidentate ligands, N-phenylpyridine-2-aldimine 14 (2) and N-{3- [4-(2-methoxyphenyl)piperazin-1-yl]propyl}pyridine-2-aldimine 15 (3), were synthesized and purified according to published protocols (Scheme 1). Rhenium was purchased from Aldrich as KReO 4 and was converted to the ReOCl 3 (PPh 3 ) 2 precursor as reported previously. 16 All compounds were characterized by IR and NMR spectroscopy.…”

Section: Methodsmentioning

confidence: 99%

“…The NMR spectra were recorded in CDCl 3 on a Bruker 500-MHz Avance DRX spectrometer using (CH 3 ) 4 Si as the internal reference. Elemental analyses for C, H, N, and S were conducted on a Perkin-Elmer 2400/II automatic elemental analyzer.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and Characterization of Novel “3 + 2” Oxorhenium Complexes, ReO[SNO][NN]

et al. 2006

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The present paper deals with the synthesis and structural characterization of novel neutral oxorhenium(V) complexes of the general formula ReO[SNO][NN]. The simultaneous action of the tridentate SNO ligand, N-(2-mercaptoacetyl)glycine (1), and the bidentate NN ligand, N-phenylpyridine-2-aldimine (2), on ReOCl3(PPh3)2 leads to the formation of two isomers 4a and 4b of the general formula ReO[SNO][NN], as a result of the different orientations of the NN ligand. In both cases, the SNO donor atoms of the tridentate ligand occupy the three positions in the equatorial plane of the distorted octahedron, whereas the oxo group is always directed toward one of the apical positions. In the first isomer, 4a, the imino nitrogen of the NN ligand occupies the fourth equatorial position and the pyridine type nitrogen is directed trans to the oxo group, while in the second isomer, 4b, the imino nitrogen of the NN ligand occupies the apical position trans to the oxo group and the pyridine type nitrogen completes the equatorial plane of the distorted octahedron. The [SNO][NN] mixed-ligand system was applied in the synthesis of the oxorhenium complex 5 in which the 1-(2-methoxyphenyl)piperazine moiety, a fragment of the true 5-HT1A antagonist WAY 100635, has been incorporated in the NN bidentate ligand (NN is N-{3-[4-(2-methoxyphenyl)piperazin-1-yl]propyl}pyridine-2-aldimine). In this case, high-performance liquid chromatography and NMR showed the existence of one isomer, 5, in which the pyridine nitrogen is trans to the oxo core, as demonstrated by crystal structure analysis.

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“…The reaction mixture was vigorously shaken and allowed to react at room temperature for sufficient time to complete the reaction (Boyd 1986). The proposed structure of the Tc-histamine complex coordinated as a Tc (V) oxocore, leading to complexes in which a TcO 3+ core exists (Jurisson et al 1986;Abrams et al 1991).…”

Section: Labeling Of Histaminementioning

confidence: 99%

Novel radiochemical and biological characterization of 99mTc-histamine as a model for brain imaging

Sanad

2014

J Anal Sci Technol

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Synthesis, characterization, and x-ray structural determinations of technetium(V)-oxo-tetradentate amine oxime complexes

Cited by 99 publications

References 2 publications

Technetium(V) Oxo Complexes of Substituted Propylene Diamine Dioxime (PnAO) Ligands: Water-Dependent Interconversion between Syn and Anti Isomers

Technetium(V) Oxo Complexes of Substituted Propylene Diamine Dioxime (PnAO) Ligands: Water-Dependent Interconversion between Syn and Anti Isomers

Synthesis and Characterization of Novel “3 + 2” Oxorhenium Complexes, ReO[SNO][NN]

Novel radiochemical and biological characterization of 99mTc-histamine as a model for brain imaging

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