Methyl group transfer on halogen oxidation of binuclear methylplatinum complexes: the mechanism of reaction and structure of a bridged platinum(IV)-platinum(II) product

Ling, Samson S. M.; Payne, Nicholas C.; Puddephatt, Richard J.

doi:10.1021/om00128a011

Cited by 22 publications

(13 citation statements)

References 5 publications

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“…The P-C distances lie in the range 1.753(14)-1.818(14) 8,, average 1.792 A. The angle at nitrogen is 142.1( 7)" and the angles around the phosphorus atoms all lie near the tetrahedral value, range 105.7(7)-115.5 (7).…”

Section: Resultsmentioning

confidence: 94%

Binuclear pentafluorophenyl complexes containing halide and/or bis(diphenylphosphino)methane (dppm) as bridging ligands. Molecular structure of [N(PPh₃)₂][Pt₂(µ-I)(µ-dppm)(C₆F₅)₄]·2CHCL₃

Casas¹,

Falvello²,

Forniés³

et al. 1993

J. Chem. Soc., Dalton Trans.

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Section: Resultsmentioning

confidence: 94%

Binuclear pentafluorophenyl complexes containing halide and/or bis(diphenylphosphino)methane (dppm) as bridging ligands. Molecular structure of [N(PPh₃)₂][Pt₂(µ-I)(µ-dppm)(C₆F₅)₄]·2CHCL₃

Casas¹,

Falvello²,

Forniés³

et al. 1993

J. Chem. Soc., Dalton Trans.

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“…1), 19 3b,20 we propose that oxidation of 3 generates a Pd III -Pd III species with a shorter Pd-Pd bond that promotes the observed methyl group transfer and disproportionation reaction (Scheme 2). 21 In summary, the Pd II and Pt II complexes described herein display unique d 8 -d 8 interactions between dicationic metal fragments that are not supported by any bridging ligands, strongly suggesting the existence of a significant metal-metal bonding character. In addition, preliminary reactivity studies suggest that such metal-metal interactions may be involved in methyl group transfer reactions.…”

mentioning

confidence: 75%

Unsupported d⁸–d⁸interactions in cationic Pd^IIand Pt^IIcomplexes: evidence for a significant metal–metal bonding character

et al. 2012

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“…The reactivity of these complexes with Cl 2 and MeI to yield dinuclear M(IV) (M = Pd, Pt) compounds and bis(arenonium) species is detailed. Of special interest is the observation of a rare mixed-valence (Pt II ,Pt IV ) species by 1 H NMR spectroscopy. − …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of the Bis-Cyclometalating Ligand 3,3‘,5,5‘-Tetrakis[(dimethylamino)methyl]biphenyl and Its Use in the Preparation of Bimetallic M(II), M(IV) (M = Pt, Pd), and Mixed-Valence Pt(II)−Pt(IV) Complexesviaa Dilithio-Derivative. Crystal Structure of the Pd Dimer [ClPd{2,6-(Me₂NCH₂)₂C₆H₂}]₂

et al. 1998

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The potentially bis-cyclometalating ligand 3,3′,5,5′-tetrakis[(dimethylamino)methyl]biphenyl, was prepared from 3,5-(Me 2 NCH 2) 2 C 6 H 3 Br in a one-pot synthesis involving lithium-halogen exchange, transmetalation, and reductive-elimination reactions. This ligand undergoes selective dilithiation in the 4 and 4′ positions of the biphenyl group to form [Li 2 {2,6-(Me 2 NCH 2) 2 C 6 H 2 } 2 ] n , which is a versatile precursor to bimetallic complexes via a double transmetalation reaction. The syntheses and characterization of the new homobinuclear Pt(II) and Pd(II) compounds, [(MeCN)Pt{2,6-(Me 2 NCH 2) 2 C 6 H 2 }-] 2 (CF 3 SO 3) 2 and [ClPd{2,6-(Me 2 NCH 2) 2 C 6 H 2 }-] 2 , is reported in addition to a novel synthetic route to the complex [ClPt{2,6-(Me 2 NCH 2) 2 C 6 H 2 }-] 2. The solid-state structure of Pd dimer was determined by single-crystal X-ray diffraction. Oxidative addition of Cl 2 to the latter Pt compound produced the bis-platinum(IV) complex [Cl 3 Pt{2,6-(Me 2 NCH 2) 2 C 6 H 2 }-] 2 , which reacts with 2 equiv of Ag(O 3 SCF 3) in MeCN solution to form [(MeCN)Cl 2 Pt{2,6-(Me 2-NCH 2) 2 C 6 H 2 }-] 2 (CF 3 SO 3) 2. This complex could also be obtained directly by reaction of the former Pt II dimer with 2 equiv of Cl 2 IPh. 1 H NMR spectroscopic studies show that mixtures of the Pt II and Pt IV dimers in acetonitrile solution are in equilibrium with a mixed-valence (Pt II ,Pt IV) species [(MeCN)Pt II {2,6-(Me 2 NCH 2) 2 C 6 H 2-C 6 H 2 (CH 2 NMe 2)-2,6}Pt IV Cl 2 (NCMe)](CF 3-SO 3) 2 , which, however, could not be isolated in pure form. The reaction of the Pt II dimer with e1 equiv of Cl 2 IPh also gave a Pt IV dimer, along with unreacted starting material and the mixed-valence complex. A reversible double CC bond formation has been achieved by reaction of the Pt II dimer with excess of methyl iodide. This procedure yields the bis(arenonium) species [IPt II {2,6-(Me 2 NCH 2) 2-1-MeC 6 H 2 }-] 2 (CF 3 SO 3) 2 in which both the Me groups derived from I-Me bond cleavage are bound to the C ipso of the aryl rings. The mono-(arenonium) compound [IPt II {2,6-(Me 2 NCH 2) 2-1-MeC 6 H 2-C 6 H 2 (CH 2 NMe 2) 2-2′,6′}Pt II ](CF 3 SO 3) 2 has been identified as an intermediate in this reaction by 1 H NMR spectroscopy.

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Methyl group transfer on halogen oxidation of binuclear methylplatinum complexes: the mechanism of reaction and structure of a bridged platinum(IV)-platinum(II) product

Cited by 22 publications

References 5 publications

Binuclear pentafluorophenyl complexes containing halide and/or bis(diphenylphosphino)methane (dppm) as bridging ligands. Molecular structure of [N(PPh₃)₂][Pt₂(µ-I)(µ-dppm)(C₆F₅)₄]·2CHCL₃

Binuclear pentafluorophenyl complexes containing halide and/or bis(diphenylphosphino)methane (dppm) as bridging ligands. Molecular structure of [N(PPh₃)₂][Pt₂(µ-I)(µ-dppm)(C₆F₅)₄]·2CHCL₃

Unsupported d⁸–d⁸interactions in cationic Pd^IIand Pt^IIcomplexes: evidence for a significant metal–metal bonding character

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Methyl group transfer on halogen oxidation of binuclear methylplatinum complexes: the mechanism of reaction and structure of a bridged platinum(IV)-platinum(II) product

Cited by 22 publications

References 5 publications

Binuclear pentafluorophenyl complexes containing halide and/or bis(diphenylphosphino)methane (dppm) as bridging ligands. Molecular structure of [N(PPh3)2][Pt2(µ-I)(µ-dppm)(C6F5)4]·2CHCL3

Binuclear pentafluorophenyl complexes containing halide and/or bis(diphenylphosphino)methane (dppm) as bridging ligands. Molecular structure of [N(PPh3)2][Pt2(µ-I)(µ-dppm)(C6F5)4]·2CHCL3

Unsupported d8–d8interactions in cationic PdIIand PtIIcomplexes: evidence for a significant metal–metal bonding character

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Binuclear pentafluorophenyl complexes containing halide and/or bis(diphenylphosphino)methane (dppm) as bridging ligands. Molecular structure of [N(PPh₃)₂][Pt₂(µ-I)(µ-dppm)(C₆F₅)₄]·2CHCL₃

Binuclear pentafluorophenyl complexes containing halide and/or bis(diphenylphosphino)methane (dppm) as bridging ligands. Molecular structure of [N(PPh₃)₂][Pt₂(µ-I)(µ-dppm)(C₆F₅)₄]·2CHCL₃

Unsupported d⁸–d⁸interactions in cationic Pd^IIand Pt^IIcomplexes: evidence for a significant metal–metal bonding character