Alternative syntheses and reactivity of platinum(II) terpyridyl acetonitrile complexes

Pappenfus, Ted M.; Burney, Jason R.; McGee, Kari A.; Lee, Garett G.W.; Jarvis, Larissa R.; Ekerholm, Daniel P.; Farah, Mohamed Guled; Smith, Lisa I.; Hinkle, Lindsay M.; Mann, Kent R.

doi:10.1016/j.ica.2010.05.060

Cited by 13 publications

(7 citation statements)

References 45 publications

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“…[Pt(tpy)(CH3CN)](CH3SO3)2 and the N-(4-ethynylphenyl) acetamide were synthesized following previously reported procedures, [36][37][38][39] while all ligand and complex synthetic procedures were carried out under nitrogen with degassed anhydrous solvents. 1 H and 13 C-{ 1 H} NMR spectra were obtained on Bruker AC 300, AV 300, AMX 400, AV 400 or DRX 500 spectrometers.…”

Section: Methodsmentioning

confidence: 99%

A luminescent europium hairpin for DNA photosensing in the visible, based on trimetallic bis-intercalators

Scarpantonio

Cotton

Giorgio

et al. 2020

Journal of Inorganic Biochemistry

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Section: Methodsmentioning

confidence: 99%

A luminescent europium hairpin for DNA photosensing in the visible, based on trimetallic bis-intercalators

Scarpantonio

Cotton

Giorgio

et al. 2020

Journal of Inorganic Biochemistry

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“…The presence of a bulky tert ‐butyl group affects the aggregation of the square‐planar platinum complex. While in several examples they impede the formation of close Pt–Pt interactions, we note however that in other cases the monomers can rotate so that the tert ‐butyl groups avoid one another, allowing short Pt–Pt separations to form within the dimers . Thus, we felt that aggregation control of Pt( t Bu 3 terpy) with our sulfide organometallic linkers would be an exciting challenge.…”

Section: Figurementioning

confidence: 99%

“…While in severale xamples they impede the formation of close Pt-Pt interactions, [8,38] we note however that in other cases the monomers can rotate so that the tert-butyl groups avoid one another,a llowing short Pt-Pt separations to form within the dimers. [39] Thus, we felt that aggregation controlo f Pt(tBu 3 terpy) with our sulfide organometallic linkers would be an exciting challenge. As described previously,t he deep red complexes [Pt(tBu 3 terpy)-(pR,R)-1][OTf] 2 (pR,R)-3,[ Pt(tBu 3 terpy)-(pS,S)-1][OTf] 2 (pS,S)-3,a nd rac-3 were obtainedf ollowing similar synthetic procedures, using [Pt(tBu 3 terpy)(CH 3 CN)][OTf] 2 as as tarting material.…”

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confidence: 99%

Highly Phosphorescent Crystals of Square‐Planar Platinum Complexes with Chiral Organometallic Linkers: Homochiral versus Heterochiral Arrangements, Induced Circular Dichroism, and TD‐DFT Calculations

Sesolis

Dubarle‐Offner

Chan

et al. 2016

Chemistry A European J

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A novel class of chiral luminescent square-planar platinum complexes with a π-bonded chiral thioquinonoid ligand is described. Remarkably the presence of this chiral organometallic ligand controls the aggregation of this square planar luminophor and imposes a homo- or hetero-chiral arrangement at the supramolecular level, displaying non-covalent Pt-Pt and π-π interactions. Interestingly these complexes are highly luminescent in the crystalline state and their photophysical properties can be traced to their aggregation in the solid state. A TD-DFT calculation is obtained to rationalize this unique behavior.

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“…Crystallographic data of trans-3 (both structures), cis-3, 10, and 15 are available from the Cambridge Crystallographic Database as file nos. CCDC 1006528 (cis-3), 1006527 (trans-3 (CH 2 Cl 2 )), 1006728 (trans-3 (CDCl 3 )), 1006727 (10), and 1006526 (15).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…The properties and reaction behavior of organonitrile transition metal complexes have been studied for more than 150 years and still are very promising topics in inorganic chemistry. − In most cases, the appropriate metal–organic complexes possess a weak metal–nitrogen bond; , therefore, they are often used as starting materials in inorganic and organometallic chemistry for the synthesis of highly functionalized or even (hetero)multimetallic transition metal compounds. ,− Due to the possibility of easy nitrile ligand replacement, such complexes play an important role in homogeneous catalysis. − Acetonitrile and benzonitrile transition metal complexes are the best studied representatives of this class of compounds. − In many cases they can easily be prepared by heating the corresponding transition metal salt in the appropriate nitrile. , In contrast, the synthesis and chemical properties of metallocenyl nitrile-based transition metal complexes are rarely described in the literature, − despite the fact that ferrocenecarbonitrile has already been reported as early as 1956, , only five years after the discovery of ferrocene in 1951 . In 2013, our research group published the synthesis of tetrakis(ferrocenecarbonitrile) copper(I) complexes, the first complexes with more than one ferrocenecarbonitrile ligand coordinated to a transition metal ion …”

Section: Introductionmentioning

confidence: 99%

From Ferrocenecarbonitriles to Ferrocenylimines: Synthesis, Structure, and Reaction Chemistry

et al. 2014

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From the reaction of [PtCl2(NCMe)2] with FcCN (1) (Fc = Fe(η5-C5H4)(η5-C5H5)) complex [PtCl2(FcCN)(NCMe)] (2) was obtained, which on subsequent treatment with 1 gave trans-[PtCl2(NCFc)2] (trans-3). The latter complex and the appropriate cis isomer (cis-3) were also accessible when [PtCl2] or [PtCl2(NCMe)2] is reacted with a 2.6-fold excess of 1. Appropriate treatment of [PtCl2(NCMe)2] with two equivalents of 1-acetyl-1′-cyanoferrocene (4) produced trans-[PtCl2(Fe(η5-C5H4CN)(η5-C5H4C(O)Me))2] (trans-5). Coordination polymer [PtCl2(Fe(η5-C5H4CN)2)] n (7) was obtained by combining [PtCl2(NCPh)2] with [Fe(η5-C5H4CN)2] (6). However, when 7 was reacted with PPh3 for deaggregation, [PtCl2(PPh3)2] was formed. Addition of FcCCLi (8-Li) to trans-3 gave pentametallic trans-[Pt(CCFc)2(NHC n BuFc)2] (10) via trans-[Pt(CCFc)2(NCFc)2] (9). When trans-3 is reacted with two equivalents of n BuLi in the absence of FcCCH (8), trans-[PtCl2(NHC n BuFc)2] (11) was obtained, which decomposed to FcC(NH) n Bu (12), giving FcC(O) n Bu (13). Electrochemical measurements of the nitrile platinum complexes show no redox separation for the oxidation of the Fc and Fe(η5-C5H4)2 moieties. Compared with the noncoordinated ferrocenecarbonitriles, a shift to higher potentials is observed. In contrast, for 10 four well-separated redox events (−185, –90, +460, +545 mV) were found, which could be assigned to the oxidation of the Fc units. UV–vis/NIR spectroscopy allowed to determine an IVCT absorption (νmax = 6495 cm–1, εmax = 270 L·mol–1·cm–1, Δν1/2 = 2270 cm–1) for 10 + , classifying this mixed-valent species as a weakly coupled class II system according to Robin and Day, while no IVCT transitions were observed for 10 n+ (n = 2, 3). The structures of trans-3, cis-3, 10, and FcC(O) t Bu (15) in the solid state were determined by single-crystal X-ray diffraction. Although the bond distances and angles of trans- 3 and cis-3 are similar, the cis isomer crystallizes as a dimer possessing Pt–Pt distances within the sum of the van der Waals radii.

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Alternative syntheses and reactivity of platinum(II) terpyridyl acetonitrile complexes

Cited by 13 publications

References 45 publications

A luminescent europium hairpin for DNA photosensing in the visible, based on trimetallic bis-intercalators

A luminescent europium hairpin for DNA photosensing in the visible, based on trimetallic bis-intercalators

Highly Phosphorescent Crystals of Square‐Planar Platinum Complexes with Chiral Organometallic Linkers: Homochiral versus Heterochiral Arrangements, Induced Circular Dichroism, and TD‐DFT Calculations

From Ferrocenecarbonitriles to Ferrocenylimines: Synthesis, Structure, and Reaction Chemistry

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