Synthesis, structure, and platinum-195 NMR solution studies of a reactive binuclear platinum(III) complex: bis(ethylenediamine)nitratonitrobis(2-pyridonato)diplatinum(2+) dinitrate hemihydrate

O’Halloran, Thomas V.; Roberts, Michael M.; Lippard, Stephen J.

doi:10.1021/ic00227a015

Cited by 59 publications

(36 citation statements)

References 6 publications

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“…89 The 195 Pt NMR chemical shifts for [ 2 ] 2+ and [ 3 ] 2+ are −76 and −216 ppm, respectively, within the region expected for a dinuclear platinum(III) complex. 52 The 140 ppm upfield shift of [ 3 ] 2+ relative to [ 2 ] 2+ is consistent with the empirical observation that softer ligands shift 195 Pt NMR resonances to more negative values. 90 The signals of [ 2 ] 2+ and [ 3 ] 2+ appear as quintets, which arise from coupling to two equivalent 14 N nuclei.…”

Section: Resultssupporting

confidence: 82%

Acetate-Bridged Platinum(III) Complexes Derived from Cisplatin

Wilson

Lippard

2012

Inorg. Chem.

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Oxidation of the acetate-bridged half-lantern platinum(II) complex, cis-[PtII(NH3)2(µ-OAc)2PtII(NH3)2](NO3)2, [1](NO3)2, with iodobenzene dichloride or bromine generates the halide-capped platinum(III) species, cis-[XPtIII(NH3)2(µ-OAc)2PtIII(NH3)2X](NO3)2, where X is Cl in [2](NO3)2, or Br in [3](NO3)2, respectively. These three complexes, characterized structurally by X-ray crystallography, feature short (≈ 2.6 Å) Pt–Pt separations, consistent with formation of a formal metal-metal bond upon oxidation. Elongated axial Pt–X distances occur, reflecting the strong trans influence of the metal-metal bond. The three structures are compared to those of other known dinuclear platinum complexes. A combination of 1H, 13C, 14N, and 195Pt NMR spectroscopy was used to characterize [1]2+–[3]2+ in solution. All resonances shift downfield upon oxidation of [1]2+ to [2]2+ and [3]2+. For the platinum(III) complexes, the 14N and 195Pt resonances exhibit decreased linewidths by comparison to those of [1]2+. Density functional theory (DFT) calculations suggest that the decrease in 14N linewidth arises from a diminished electric field gradient (EFG) at the 14N nuclei in the higher valent compounds. The oxidation of [1](NO3)2 with the alternative oxidizing agent, bis(trifluoroacetoxy) iodobenzene, affords the novel tetranuclear complex, cis-[(O2CCF3)PtIII(NH3)2(µ-OAc)2PtIII(NH3)(µ-NH2)]2(NO3)4, [4](NO3)4, also characterized structurally by X-ray crystallography. In solution, this complex exists as a mixture of species, the identities of which are proposed.

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Section: Resultssupporting

confidence: 82%

Acetate-Bridged Platinum(III) Complexes Derived from Cisplatin

Wilson

Lippard

2012

Inorg. Chem.

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“…1450 and 1100 cm -1 in their IR spectra. [57] Similar bands for κ-NO 2 have been observed in the complexes [Pt(NO 2 ) 2 (cisPh 2 PCH=CHPPh 2 )] [58] and [Pt(en) 2 (µ- [59] and the mode of coordination has been confirmed by X-ray crystallography in the latter. (36) and P(OPh) 3 (37) were isolated, usually as colourless or off-white solids; exceptionally, those derived from o-, m-and p-toluidine were obtained as red or purple solids, probably owing to the formation of organic oxidation products in the presence of traces of the Ag + oxidant.…”

Section: Neutralsupporting

confidence: 73%

Selective Cleavage by Acids of One Metal–Carbon σ‐Bond of a Bis(ortho‐platinated) Triarylphosphane: A ³¹P NMR trans‐Influence Series Based on the Unit Pt(κ²‐C₆H₃‐5‐Me‐2‐PPh₂)(PPh₂‐4‐tol)

et al. 2008

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Treatment of the bis(chelate) complex cis-[Pt(κ 2 -C 6 H 3 -5-Me-2-PPh 2 ) 2 ] (1) with strong acids causes selective cleavage of one of the metal-aryl bonds to give cis-[PtX(κ 2 -C 6 H 3 -5-Me-2-PPh 2 )(PPh 2 -4-tol)] [X = Cl (2), Br (3), I (4), ONO 2 (5) and OCOCF 3 (6)], from which a series of neutral and cationic derivatives can be derived by metathetical reactions. The complexes 2 and 6 rearrange spontaneously to the corresponding trans isomers, this reaction being promoted by CO. The J(Pt-P) values for the phosphorus atom of the four-membered ring can be ordered to establish a trans-influence series of anionic ligands X and neutral ligands L, which correlates well with, but is more extensive than, that based earlier on PtMe(dppe) complexes. Single-crystal X-ray structural analysis of trans-[Pt(κ 1 -OCOCF 3 )(κ 2 -C 6 H 3 -5-Me-2-PPh 2 )(PPh 2 -4-tol)] (trans-

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“…The platinum(III) binuclear complexes are structurally classified into three groups according to the number of the bridging ligands [1][2][3]: (1) four bridged ''lantern-type'' complexes coordinated by symmetric [9][10][11][12][13][14][15][16][17] or asymmetric bridging ligands [18,19] and (2) ''platinum blues''-derived amidato-bridged complexes having two bridging ligands [1][2][3][20][21][22][23][24] (Chart 1), and (3) diplatinum(III) complexes with no bridging ligand (very rare) [25,26]. Most of the complexes of group (1) and (2) are considerably stable in solid and/or in solution, and have been widely studied.…”

Section: Introductionmentioning

confidence: 99%

Kinetics and mechanisms of the axial ligand substitution reactions of platinum(III) binuclear complexes with halide ions

Iwatsuki

Ishihara

Matsumoto

2006

Science and Technology of Advanced Materials

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The axial water ligand substitution reaction on the head-to-head (HH) and head-to-tail (HT) amidato-bridged cis-diammineplatinum(III) binuclear complexes, HH-and HT-[Pt 2 (NH 3 ) 4 (m-amidato) 2 (OH 2 ) 2 ] 4+ (amidato ¼ a-pyridonato, a-pyrrolidonato, or pivalamidato), with halide ions (X À ¼ Cl À , Br À ) in acidic aqueous solution reveals a consecutive 2-step kinetics under the pseudo first-order conditions of a large excess concentration of halide ion relative to that of the complex ðC X À bC Pt Þ, corresponding to formation of the monohalo (step 1) and the dihalo complexes (step 2). The first substitution step of all the HH and HT diaqua dimers consists of two parallel reaction pathways: one is the simple substituion path of one of the coordinated aqua ligands with X À , and the other is the replacement in the aquahydroxo complex which is the conjugate base of the diaqua dimer. In step 2, there are three reaction pathway patterns: the direct substitution path, the path via a coordinatively unsaturated intermediate, and the unusual path of OH À replacement.Step 2 proceeds via either one or two paths of the three depending on the nature of the halide ion as well as the bridging ligand. On the other hand, the substitution reaction of the hydrogenphosphato-bridged lantern-type complex, [Pt 2 (m-HPO 4 ) 4 (OH 2 ) 2 ] 2À proceeds in 1-step at C X À bC Pt , in which the first aqua ligand substitution to form the monohalo species is rate-determining and the monohalo species is in rapid equilibrium with the dihalo complex. The rate-determining step consists of parallel pathways similar to step 1 in the amidato-bridged complex systems. r

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Synthesis, structure, and platinum-195 NMR solution studies of a reactive binuclear platinum(III) complex: bis(ethylenediamine)nitratonitrobis(2-pyridonato)diplatinum(2+) dinitrate hemihydrate

Cited by 59 publications

References 6 publications

Acetate-Bridged Platinum(III) Complexes Derived from Cisplatin

Acetate-Bridged Platinum(III) Complexes Derived from Cisplatin

Selective Cleavage by Acids of One Metal–Carbon σ‐Bond of a Bis(ortho‐platinated) Triarylphosphane: A ³¹P NMR trans‐Influence Series Based on the Unit Pt(κ²‐C₆H₃‐5‐Me‐2‐PPh₂)(PPh₂‐4‐tol)

Kinetics and mechanisms of the axial ligand substitution reactions of platinum(III) binuclear complexes with halide ions

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Synthesis, structure, and platinum-195 NMR solution studies of a reactive binuclear platinum(III) complex: bis(ethylenediamine)nitratonitrobis(2-pyridonato)diplatinum(2+) dinitrate hemihydrate

Cited by 59 publications

References 6 publications

Acetate-Bridged Platinum(III) Complexes Derived from Cisplatin

Acetate-Bridged Platinum(III) Complexes Derived from Cisplatin

Selective Cleavage by Acids of One Metal–Carbon σ‐Bond of a Bis(ortho‐platinated) Triarylphosphane: A 31P NMR trans‐Influence Series Based on the Unit Pt(κ2‐C6H3‐5‐Me‐2‐PPh2)(PPh2‐4‐tol)

Kinetics and mechanisms of the axial ligand substitution reactions of platinum(III) binuclear complexes with halide ions

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Selective Cleavage by Acids of One Metal–Carbon σ‐Bond of a Bis(ortho‐platinated) Triarylphosphane: A ³¹P NMR trans‐Influence Series Based on the Unit Pt(κ²‐C₆H₃‐5‐Me‐2‐PPh₂)(PPh₂‐4‐tol)