Synthesis and electrochemistry of [Pt(tame)2]4+: crystallographic analysis of bis[1,1,1-tris(aminomethyl)ethane-N,N ′]platinum(II) bis(tetrachlorozincate) dihydrate

Brown, Kylie N.; Hockless, David C. R.; Sargeson, Alan M.

doi:10.1039/a901725i

Cited by 11 publications

(7 citation statements)

References 12 publications

(11 reference statements)

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“…This is in agreement with the previously studied redox behavior of octahedral Pt IV amine-halide compounds whereby two coordination sites are vacated and a square planar geometry is adopted to accommodate the resulting d 8 Pt II center. This process is commonly seen in the activation of Pt IV anticancer agents. − Furthermore, Sargeson et al have reported on [Pt(tame) 2 ] 4+ , a complex with a related structure, that undergoes the same conformational change upon reduction …”

Section: Resultsmentioning

confidence: 93%

“…[56][57][58] Furthermore, Sargeson et al have reported on [Pt(tame) 2 ] 4þ , a complex with a related structure, that undergoes the same conformational change upon reduction. 59 It should also be noted that the potential required for the reduction of the Pt IV center within a particular C ∧ N series increases as a function of the donor ability of the N ∧ N ligand in the order of dFbpy < bpy < dMeObpy. This variation corresponds to an increasing bond strength between the N ∧ N ligand and Pt and correlates with the raised energy of the e g * orbital.…”

Section: Jenkins and Bernhardmentioning

confidence: 99%

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Synthesis and Characterization of Luminescent Bis-Cyclometalated Platinum^IV Complexes

Jenkins

Bernhard

2010

Inorg. Chem.

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Presented is the synthesis and characterization of a series of luminescent heteroleptic bis-cyclometalated platinum(IV) complexes. An oxidation-facilitated cyclometalation is employed to convert platinum(II) pendant species into bis-cyclometalated platinum(IV) dichlorides, which are transformed into the tris-chelated diimine complexes through ligand substitution. The structure-property relationship is probed by judiciously varying substituents on both the C(∧)N and the N(∧)N ligands resulting in a family of complexes exhibiting blue emission, long excited-state lifetimes, and highly efficient oxygen quenching. Excited-state properties are corroborated by static and time-dependent density-functional theory calculations of both the singlet and the triplet state.

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Section: Resultsmentioning

confidence: 93%

Section: Jenkins and Bernhardmentioning

confidence: 99%

Synthesis and Characterization of Luminescent Bis-Cyclometalated Platinum^IV Complexes

Jenkins

Bernhard

2010

Inorg. Chem.

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“…The mechanistic proposal for the trans to cis rearrangement has precedent in the reduction of the [Pt(en) 3 ] 4ϩ ion. 20 In neutral conditions, [Pt(en) 2 ] 2ϩ and dissociated 1,2-ethanediamine are produced but in acidic conditions, the di-protonated bismonodentate product [Pt(en)(enH) 2 ] 4ϩ has been isolated. In this instance, protonation of the pendant amines clearly slows the subsequent intramolecular amine addition to give the more stable square planar [Pt(en) 2 ] 2ϩ ion and free ligand.…”

Section: Discussionmentioning

confidence: 99%

Specificity in template syntheses of hexaaza-macrobicyclic cages: [Pt(Me5-tricosatrieneN6)]4+ and [Pt(Me5-tricosaneN6)]4+Electronic supplementary information (ESI) available: tables of hydrogen atom position parameters, displacement parameters and torsional angles for all crystal structures and some electrochemical data and NMR spectral data for the hydrogenation of [Pt(Me5-tricosatrieneN6)]Cl4. See http://www.rsc.org/suppdata/ob/b2/b212326f/

et al. 2003

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The racemic C3 hexadentate cage complex, [Pt(Me5-tricosatrieneN6)]Cl4 (1,5,9,13,20-pentamethyl-3,7,11,15,18,22-hexaazabicyclo[7.7.7]tricosa- 3,14,18-triene)platinum(IV) tetrachloride), was synthesised stereospecifically and regiospecifically from a reaction of the bis-triamine template [Pt(tamc)2]Cl4 (bis[1,1,1-tris(aminomethyl)ethane]- platinum(IV) tetrachloride) with formaldehyde and then propanal, in acetonitrile under basic conditions. Largely, one racemic diastereoisomer was obtained in a surprisingly high yield (approximately 50%), even though the molecule has seven chiral centres. The origins of the stereoselective synthesis are addressed. The crystal structure of [Pt(Me5-tricosatrieneN6)]-(ZnCl4)1.5Cl.2H2O showed that all three imines were attached to one tame fragment with a chiral amine site ([symbol: see text] SSS, delta RRR) and a chiral methine carbon site ([symbol: see text] RRR, delta SSS) on each ligand strand. The PtN6(4+) moiety had a slightly distorted octahedral configuration with the two types of Pt-N bonds related to the imine and the amine donors, 2.050(7) and 2.072(6) A, respectively. Treatment with sodium borohydride (15 s, 20 degrees C) at pH approximately 12.5 reduced the imine groups, but not the Pt(IV) ion, producing a C3 saturated ligand complex [Pt(Me5-tricosaneN6)]Cl4 ((1,5,9,13,20- pentamethyl-3,7,11,15,18,22- hexaazabicyclo[7.7.7]tricosane)platinum(IV)tetrachloride). X-ray crystallographic analysis showed that the average Pt-N bond distance in the cation increased upon imine reduction to 2.10 (av) A. The cyclic voltammograms of the two cage complexes displayed irreversible two-electron reduction waves in aqueous media and a approximately 0.3 V shift to more positive potentials compared to that of the smaller cavity sar (3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane) analogue. After reduction, net dissociation of one strand of the cage was also evident, to give unstable square planar Pt(II) macrocyclic products.

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“…N , N -dimethylformamide (DMF), acetonitrile, and dichloromethane were distilled over CaH 2 . 1,1,1-(Trisaminomethyl)ethane (TAME) was purchased from Fluka AG or synthesized according to published procedures . The perchlorate salts were prepared from the corresponding oxides (Rhodia and Aldrich, 99.99%) and dried according to published procedures .…”

Section: Methodsmentioning

confidence: 99%

Unsymmetrical Tripodal Ligand for Lanthanide Complexation: Structural, Thermodynamic, and Photophysical Studies

Aroussi¹,

Dupont²,

Bérnardinelli

et al. 2009

Inorg. Chem.

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Two tridentate and one bidentate binding strands have been anchored on a carbon atom to provide a new unsymmetrical tripodal ligand L for Ln(III) coordination. The ligand itself adopts a single conformation in solution stabilized by intramolecular hydrogen bonds evidenced in the solid state. The reaction of L with trivalent lanthanides provides different coordination complexes depending on the metal/ligand ratio. The speciation studies with selected lanthanides were performed in solution by means of NMR, ESMS, and spectrophotometric titrations. Differences in coordination properties along the lanthanide series were evidenced and may be associated with the changes in the ionic size. However, thermodynamic stability constants for the species of the same stoichiometry do not significantly vary. In addition, the structure of the dinuclear complex [Eu(2)L(2)](6+) has been elucidated in the solid state, where the complex crystallizes predominantly as an M-isomer. The crystal structure shows the coordination of two different ligands to each europium cation through tridentate strands, and the europium nine-coordinate sphere is completed with three solvent molecules. Finally, the results of photophysical investigations of [Eu(2)L(2)](6+) are in close agreement with the structural parameters determined by crystallography.

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Synthesis and electrochemistry of [Pt(tame)2]4+: crystallographic analysis of bis[1,1,1-tris(aminomethyl)ethane-N,N ′]platinum(II) bis(tetrachlorozincate) dihydrate

Cited by 11 publications

References 12 publications

Synthesis and Characterization of Luminescent Bis-Cyclometalated Platinum^IV Complexes

Synthesis and Characterization of Luminescent Bis-Cyclometalated Platinum^IV Complexes

Unsymmetrical Tripodal Ligand for Lanthanide Complexation: Structural, Thermodynamic, and Photophysical Studies

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Synthesis and electrochemistry of [Pt(tame)2]4+: crystallographic analysis of bis[1,1,1-tris(aminomethyl)ethane-N,N ′]platinum(II) bis(tetrachlorozincate) dihydrate

Cited by 11 publications

References 12 publications

Synthesis and Characterization of Luminescent Bis-Cyclometalated PlatinumIV Complexes

Synthesis and Characterization of Luminescent Bis-Cyclometalated PlatinumIV Complexes

Unsymmetrical Tripodal Ligand for Lanthanide Complexation: Structural, Thermodynamic, and Photophysical Studies

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Synthesis and Characterization of Luminescent Bis-Cyclometalated Platinum^IV Complexes

Synthesis and Characterization of Luminescent Bis-Cyclometalated Platinum^IV Complexes