Phosphorus-31, cadmium-113 and mercury-199 N.M.R. studies on dithiolate complexes of cadmium and mercury and their phosphine adducts

Bond, Alan M.; Colton, R.; Dakternieks, Dainis; Dillon, Michael L.; Hauenstein, Jennifer; Moir, J. E.

doi:10.1071/ch9811393

Cited by 34 publications

(2 citation statements)

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“…Potassium O , O ′-di(cyclohexyl)dithiophosphate ( Kctp ) and potassium O , O ′-di(butyl)dithiophosphate ( Kbtp ) were prepared in quantitative yield by published method with slight modification. − Potassium carbonate (10 mmol, 1.38 g) was added to a mixture of phosphorus pentasulfide (2.5 mmol, 1.11 g) in desired alcohol (5 mL, excess) at 60 °C. The reaction mixture was stirred for 2 h at 80 °C.…”

Section: Methodsmentioning

confidence: 99%

Cyclometalated Platinum(II) Complexes Bearing Bidentate O,O′-Di(alkyl)dithiophosphate Ligands: Photoluminescence and Cytotoxic Properties

Fereidoonnezhad¹,

Kaboudin

Mirzaee³

et al. 2017

Organometallics

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Mononuclear complexes [Pt(ppy)(S∧S)] (1a, S∧S = O,O′-di(cyclohexyl)dithiophosphate (ctp); 2a, S∧S = O,O′-di(butyl)dithiophosphate (btp)) and [Pt(bzq)(S∧S)] (1b, S∧S = ctp; 2b, S∧S = btp) have been prepared by the reaction of precursor complexes [Pt(C∧N)Cl(dmso)], C∧N = deprotonated form of 2-phenylpyrdine (ppy) and 7,8-benzoquinoline (bzq), and potassium salt of S∧S ligands. All complexes were characterized by NMR spectroscopy, and the structure of 2b was further identified by single crystal X-ray determination. Although the complexes are not luminescent in solution at ambient temperature, they become strong emissive materials (bright green) in solid state (at room temperature) with high quantum yields and long lifetimes in the microsecond domain. In frozen glass state or at low temperature (solid state), these complexes become better emissive in relation to room temperature. UV–vis spectra, supported by TD-DFT calculations, indicate that 1ILCT (intraligand charge transfer) predominates over the other transitions (L = C∧N cyclometalated ligand). Accordingly, 1 and 2 exhibit structured emission bands which display a large involvement of 3LCCT (ligand-centered charge transfer) with lower contribution of 3MLCT (metal to ligand charge transfer) transition in the excited states. Also, biological activities of 1 and 2 were evaluated against three human cancer cell lines including A549 (human lung cancer), SKOV3 (human ovarian cancer), and MCF-7 (human breast cancer). 2a presented an effective potent cytotoxic activity regarding to the cell lines. The cellular localization of 1a and 2a in MCF-7 human cells was investigated by fluorescence microscopy.

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Section: Methodsmentioning

confidence: 99%

Cyclometalated Platinum(II) Complexes Bearing Bidentate O,O′-Di(alkyl)dithiophosphate Ligands: Photoluminescence and Cytotoxic Properties

Fereidoonnezhad¹,

Kaboudin

Mirzaee³

et al. 2017

Organometallics

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“…CoL3 + e" -[CoL3]" (8) [CoL3]" -» CoL2 + [L]" (9) In dichloromethane no exchange reactions were observed with short-time-scale polarographic experiments in the absence of oxygen as described above. In long-time-scale electrolysis experiments ligand-exchange reactions are readily performed at 20 °C by simultaneous electrochemical reduction of CoL3 and CoL'3 (33) MacDonald, C. G.; Shannon, J. S. Aust.…”

Section: Resultsmentioning

confidence: 87%

Investigations of mixed-ligand cobalt dithiocarbamate complexes by cobalt-59 nuclear magnetic resonance spectroscopy, mass spectrometry, and electrochemistry

Bond¹,

Colton²,

Moir³

et al. 1985

Inorg. Chem.

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Tris(dithiocarbamate) complexes of cobalt(III), CoL3 and CoL'3 (where L and L' are different dithiocarbamato ligands), undergo ligand exchange at elevated temperatures both in an inert organic solvent and in the solid state to give CoL2L' and CoLL',. The mixed-ligand complexes may also be prepared by methods based on controlled-potential electrochemical oxidation or reduction of cobalt(II1) dithiocarbamate complexes. In contrast to these preparative-scale electrolyses, short-time-scale voltammetric and polarographic data for oxidation and reduction exhibit independent responses for the mixed-ligand complexes, implying that the formally cobalt(1V) and cobalt(I1) mixed-ligand species undergo slow rather than rapid ligand exchange. Cobalt-59 NMR spectroscopy and electrochemistry in CHIClz solution and mass spectrometry are useful techniques to illustrate ligand exchange. Cobalt-59 chemical shifts of the dithiocarbamate complexes cover a wide range and allow identification of the mixed-ligand species in many reaction mixtures as the ligand exchange for the oxidation state I11 complexes is slow on the NMR (and synthetic) time scales at ambient temperatures. Generally, 59C0 NMR chemical shifts do not correlate in a simple linear fashion with electrochemical Eo data (or with I3C NMR data), implying that steric effects influence the two techniques in different ways. However, for the mixed-ligand series CoL3, CoL,L', CoLL',, and COL'~, the Eo and s9C0 chemical shifts do correlate exceedingly well. Positive and negative ion mass spectra of CoL3 species generally show the molecular ions [CoL31t. and [CoL3]-., respectively, but the most abundant ions are [ C O L~]~-and [CoLJ.. Mass spectrometric examination of mixtures of CoL, and COL'~ show evidence of ligand exchange. Mass spectrometry in the gas phase and electrochemical data show interesting correlations.

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NMR of Metal Nuclides Part II: the Transition Metals

Dechter

1985

Progress in Inorganic Chemistry

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Phosphorus-31, cadmium-113 and mercury-199 N.M.R. studies on dithiolate complexes of cadmium and mercury and their phosphine adducts

Cited by 34 publications

References 0 publications

Cyclometalated Platinum(II) Complexes Bearing Bidentate O,O′-Di(alkyl)dithiophosphate Ligands: Photoluminescence and Cytotoxic Properties

Cyclometalated Platinum(II) Complexes Bearing Bidentate O,O′-Di(alkyl)dithiophosphate Ligands: Photoluminescence and Cytotoxic Properties

Investigations of mixed-ligand cobalt dithiocarbamate complexes by cobalt-59 nuclear magnetic resonance spectroscopy, mass spectrometry, and electrochemistry

NMR of Metal Nuclides Part II: the Transition Metals

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