Reactivity of Chelated Dinuclear Platinum(ii) Complexes

Reactivity of Chelated Dinuclear Platinum(ii) Complexes
Author: Allen Mambanda
Publisher: LAP Lambert Academic Publishing
Total Pages: 252
Release: 2012
Genre:
ISBN: 9783847378907

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The search for new Pt(II) metal drugs is underpinned by an in-depth understanding of the factors controlling the bio-reactivity of the Pt(II) pharmaceuticals. An emerging class of compounds which has shown improved antitumour activity is the multinuclear Pt(II) complexes, epitomized by the favourable reactivity profile of BBR3464 from Prof. Farrell's labs. Kinetic data of multinuclear Pt(II) compounds is not extensive. This book, reports the substitution reactions of bis(2-pyridylmethyl)amine-chelated dinuclear Pt(II) complexes linked by diamine bridges. The reactions were studied under pseudo first-order conditions as a function of concentration of nucleophiles and temperature using stopped-flow and UV-visible spectroscopic techniques. In general, the substitution of the coligand by the sulfur containing nucleophiles proceeds via a two-step reaction pathway which is associatively activated. In the studied sets of Pt(II) dinuclears, substitution of the coligands is controlled mainly by steric effects, derived from the molecular conformations of the metal complexes and to a lesser extent by electronic effects. Experimental data is well supported by Quantum mechanical calculations.

DESIGN, SYNTHESIS, PHOTOPHYSICAL, AND ELECTROCHEMICAL STUDIES OF NOVEL CYCLOMETALATED PYRAZOLATE-BRIDGED DINUCLEAR PLATINUM(II) COMPLEXES

DESIGN, SYNTHESIS, PHOTOPHYSICAL, AND ELECTROCHEMICAL STUDIES OF NOVEL CYCLOMETALATED PYRAZOLATE-BRIDGED DINUCLEAR PLATINUM(II) COMPLEXES
Author: Arnab Chakraborty
Publisher:
Total Pages: 154
Release: 2014
Genre: Electrochemical analysis
ISBN:

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The present dissertation describes the synthesis, photophysical, and electrochemical properties of a library of pyrazolate-bridged dinuclear cyclometalated platinum(II) complexes. All the complexes investigated here were synthesized with complete characterization. Both the steady state, as well as the time-resolved photophysical techniques employed during the study, helped in defining the photophysical behavior exhibited by such complexes. All the dinuclear Pt(II) complexes discussed here can be expressed by a general formula [Pt(C^N)(µ-R2pz)]2; where C^N is a cyclometalating ligand, and R2Pz are various 3,5-disubstituted pyrazolates. The bridging pyrazolates initiates the metal-metal interaction by building up steric strain within the resulting A-frame topology of the complexes. All the Pt(II) complexes are strongly emissive at room temperature. The influence of the nature of cyclometalating ligand, and the bridging pyrazolates on the photophysical and electrochemical behavior displayed by the complexes were thoroughly investigated. Both room temperature and low temperature measurements aided in distinguishing the nature of lowest energy emissive state present in such complexes. The second part of this dissertation merges our research interest in metal-organic light harvesting chromophores and MLCT complexes with extended lifetime. The dinuclear platinum(II) complexes investigated, have a 4-piperidinyl-1,8-naphthalimide (PNI) unit covalently attached to the cyclometalating 2-phenylpyridine ligand. The resulting bichromophoric complex displayed an enhanced light harvesting ability as compared to the parent dimers. Our study is an effort towards understanding the influence of increased metal-metal interaction on the establishment of a thermal equilibrium between the 3PNI and the 3MMLCT excited states.

Reactivity of Dimethylplatinum(II) Complexes

Reactivity of Dimethylplatinum(II) Complexes
Author: Muhieddine Ahmad Safa
Publisher:
Total Pages: 528
Release: 2011
Genre:
ISBN:

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This thesis describes a study of dimethylplatinum(II) and dimethylplatinum(IV) complexes containing bidentate nitrogen donor ligands. This work deals with oxidative addition, and reductive elimination chemistry, and it focuses on synthesis, characterization, and reaction mechanisms in studies of these complexes. The compound [PtMe2(bpe)], bpe = 1,2-bis(2-pyridyl)ethane, is easily oxidized to give octahedral organoplatinum(IV) complexes and the subsequent chemistry is profoundly influenced by the accompanying strain induced in the 7-membered Pt(bpe) chelate ring. On reaction of [PtMe2(bpe)] with HCl, the initial product [PtHClMe2(bpe)] undergoes reductive elimination of methane to form [PtClMe(bpe)]. In contrast, methyl iodide reacts with [PtMe2(bpe)] to give [PtIMe3(bpe)], and this decomposes by loss of the bpe ligand to give the cubane [(PtIMe3)4] and not by reductive elimination. Finally, a new class of platinum(IV) double cubane clusters was obtained on oxidation of complex [PtMe2(bpe)] with either hydrogen peroxide to give [Pt4( -OH)4(3-OH)2Me10], as a mixed complex with [PtMe2(CO3)(bpe)], or with oxygen in methanol to give [Pt4( -OH)2( -OMe)2(3-OMe)2Me10]. The oxidation of the complex [PtMe2(bps)], bps = bis(2-pyridyl)-dimethylsilane, by oxygen, hydrogen peroxide or dibenzoyl peroxide in the presence of water or alcohol gives the complex cation, [PtMe3(k3-N, N, O-HOSiMe(2-C5H4N)2)]+, in a reaction involving easy cleavage of a methylsilicon bond. Treatment of the complex [PtMe2(bps)] with B(C6F5)3 in trifluoroethanol in air gives the complex [Me(bps)Pt-OSiMe(2-C5H4N)2PtMe3]+ [B(OCH2CF3)(C6F5)3]-. The unique binuclear platinum complex is formed via the competitive methyl platinum group cleavage from [PtMe2(bps)] by the acid H[B(OCH2CF3)(C6F5)3] to give the platinum(II) fragment and oxidation by air to give the platinum(IV) fragment. Combination of the two units then gives the binuclear complex which involves a very easy methylsilicon group cleavage reaction. The platinum(II) complexes containing five-membered heterocyclic imidazole ligands show high reactivity to a broad variety of alkyl halides, peroxides, and halogens forming stable platinum(IV) complexes. The dimethylplatinum(II) complex [PtMe2{(mim)2C=CH2}], (mim)2C=CH2 = 1,1-bis(1-methylimidazole-2-yl)ethene reacts with dichloromethane to give the dimethylplatinum(IV) complex [PtCl(CH2Cl)Me2{(mim)2C=CH2}]. The product exists as a mixture of two isomers, the cis isomer as the kinetic product and the trans isomer as the thermodynamic product. The dimethylplatinum(II) complex [PtMe2(DECBP)], DECBP = 4,4'-diethoxycarbonyl- 2-2'-bipyridine], undergoes easy oxidative addition to the corresponding platinum(IV) complexes. The reactions of the complex [PtMe2(DECBP)] with alkyl bromides RCH2Br, which have hydrogen bond donor or acceptor functional groups, result in the formation of stable platinum(IV) complexes. Those complexes self-assemble in the solid state to form supramolecular polymers via the intermolecular OH---O=C, N-H---Br, OH---BrPt, interactions, with other predicted interactions such as the -stacking, and the C(H)---BrPt secondary weak interactions.

Hard and Soft Acids and Bases

Hard and Soft Acids and Bases
Author: Ralph G. Pearson
Publisher: Hutchinson Ross Publishing Company
Total Pages: 500
Release: 1973
Genre: Science
ISBN:

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