Novel Technetium and Rhenium Complexes with Multidentate Nitrogen and Sulfur Donor Ligands

Gerber, Thomas; Kemp, H. J.; Preez, Jan du; Bandoli, G.

doi:10.1524/ract.1993.63.special-issue.129

Cited by 10 publications

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“…Their appearance, coupled with the reversibility of the reduction waves, points to the formation of electrochemically generated transient intermediates sensitive to their surroundings that can be used to explore the electrochemical behaviour of various substrates toward fac-[Re-(CO) 3 (dpkdnph)Cl] in a procedure similar to that reported for fac-[Re(CO) 3 (dpk)Cl]. [17,18] (11)°is of the same order as the 84.6°bite angles observed for the dpkO,OH in [ReOCl 2 (dpkO,OH)], [23] and is larger than the 74.3°reported for bipy in fac-[Re(CO) 3 -(bipy)(OPOF 2 )]. [24] These results reveal that the six-membered metallacyclic ring in rhenium compounds with polypyridyl-like ligands is less constrained than the fivemembered metallacyclic ring in rhenium compounds with α-diimine ligands.…”

Section: Resultsmentioning

confidence: 85%

Synthesis, Characterization and Structural Studies on the First Rhenium Complex with Di(2-pyridyl) Ketone 2,4-Dinitrophenylhydrazone (dpkdnph),fac-[Re(CO)3(dpkdnph)Cl]

Bakir

2002

Eur. J. Inorg. Chem.

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When di(2-pyridyl) ketone 2,4-dinitrophenylhydrazone (dpkdnph) was allowed to react with [Re(CO) 5 Cl] in refluxing toluene fac-[Re(CO) 3 (dpkdnph)Cl] was formed in good yield. Spectroscopic measurements on fac-[Re(CO) 3 -(dpkdnph)Cl] revealed strong solvent dependence as manifested by the high sensitivity of its electronic absorption spectra to solvent variation. Electrochemical measurements on fac-[Re(CO) 3 (dpkdnph)Cl] in DMF show electrochemical properties with quasi-reversible reductions following an irreversible one-electron transfer. Structural studies on a brown

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Section: Resultsmentioning

confidence: 85%

Synthesis, Characterization and Structural Studies on the First Rhenium Complex with Di(2-pyridyl) Ketone 2,4-Dinitrophenylhydrazone (dpkdnph),fac-[Re(CO)3(dpkdnph)Cl]

Bakir

2002

Eur. J. Inorg. Chem.

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“…Frequently the coordinated dpk undergoes nucleophilic addition of water or an alcohol at the carbonylic carbon atom to form the diol or the corresponding hemiacetal, (NC 5 H 4 ) 2 C(OR)(OH), which deprotonated and acts as a mononegative, tridentate N,O,N-donor ligand (Fig.1). The three donor atoms may be coordinated to one metal atom [14][15][16] or to two metal atoms [17][18][19][20]. The N,O,N-tridentate binding mode results in the loss of electronic withdrawing properties of the ligand and enhances the electron density around the metal center [5].…”

Section: Introductionmentioning

confidence: 99%

Reactions of Dipyridylketone With Group 8 Metal Carbonyls in Different Media

Khalil

2008

Al-Azhar Bulletin of Science

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Reaction of di-(2-pyridyl)ketone (dpk) with [M 3 (CO) 12 ], M =Ru or Os in dioxan under reduced pressure gave the tricarbonyl derivative [Ru(CO) 3 (dpk)] (1) and [Os(CO) 3 (dpk)] (2). When these reactions were carried out in benzene/ethanol 1:1 (v:v) under reflux and reduced pressure gave the binuclear ruthenium complex [Ru 2 (CO) 4 (-CO)( 3 -dpkO,Oeth) 2 ] (3), where  3 -dpkO,Oeth is N,O,N-ethoxybis(2-pyridyl)-methanolato and the mononuclear [Os(CO) 3 ( 3 -dpkO,Oeth) (4). All complexes were characterized by elemental analysis, infrared, mass and 1 H NMR spectroscopy. The spectroscopic measurements indicated that in dioxane as solvent the dpk act as bidentate ligand while in benzene/ethanol solution the dpk act as tridentate ligand. The magnetic measurements revealed that the complexes (3) and (4) are paramagnetic with change in the formal oxidation state of the ruthenium and osmium atoms from zero to +1 via oxidative addition of the OH group to ruthenium or osmium with a proton displacement to give a low-spin d 7 electronic configuration The UV-Vis studies of the complexes showed blue shift compared to the ligand confirming complex formation.

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“…We have studied Re(V) complexes with bidentate heterocyclic nitrogen-donor ligands for some time [3][4][5][6][7][8]. As an extension of these studies we have investigated Re(V) complexes formed with 2,2 0 -dipyridylamine (dpa).…”

Section: Introductionmentioning

confidence: 99%

2,2′-dipyridylamine complexes of rhenium(V)

Gerber

Abrahams

Mayer

et al. 2003

Journal of Coordination Chemistry

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The reactivity of oxorhenium(V) precursors with the potentially N,N-donor ligand 2,2 0 -dipyridylamine (dpa) has been investigated. Reaction of a two-fold molar excess of dpa with trans-[ReO(OEt)Cl 2 (PPh 3 ) 2 ] in ethanol led to the isolation of [ReOCl 2 (OEt)(dpa)] (1). Spectroscopic measurements indicate that dpa is coordinated as a bidentate in the equatorial plane cis to the oxo group, with the ethoxide in the trans position. Treatment of trans-[ReOCl 3 (PPh 3 ) 2 ] with a tenfold molar excess of dpa in ethanol at reflux yielded the trans-dioxo complex [ReO 2 (dpa) 2 ]Cl (2), but with a twofold molar excess (-O)[{ReOCl 2 (dpa)} 2 ] (3a) was isolated. The latter reaction with (n-Bu 4 N)[ReOCl 4 ] as starting material in ethanol at room temperature led to a dark green product, also with the formulation (-O)[{ReOCl 2 (dpa)} 2 ] (3b). These compounds were characterised by common spectroscopic techniques, and the crystal structures of 2 Á 3H 2 O, 3a and 3b Á 2DMSO were determined. The structure of 3b presents a nearly linear O¼Re-O-Re¼O group, with the two [ReOCl 2 (dpa)] halves of the dimer rotated by 180.0 about the Re-O-Re fragment away from an eclipsed conformation. In 3a, the two halves are only rotated by 61.4 .

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Novel Technetium and Rhenium Complexes with Multidentate Nitrogen and Sulfur Donor Ligands

Cited by 10 publications

References 0 publications

Synthesis, Characterization and Structural Studies on the First Rhenium Complex with Di(2-pyridyl) Ketone 2,4-Dinitrophenylhydrazone (dpkdnph),fac-[Re(CO)3(dpkdnph)Cl]

Synthesis, Characterization and Structural Studies on the First Rhenium Complex with Di(2-pyridyl) Ketone 2,4-Dinitrophenylhydrazone (dpkdnph),fac-[Re(CO)3(dpkdnph)Cl]

Reactions of Dipyridylketone With Group 8 Metal Carbonyls in Different Media

2,2′-dipyridylamine complexes of rhenium(V)

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