Synthese zweikerniger Platin‐Verbindungen mit 1,4‐Phenylen‐Brücke

Müller, Wolf‐Dieter; Brune, Hans Albert

doi:10.1002/cber.19861190235

Cited by 17 publications

(4 citation statements)

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“…Reaction of 2.2 equiv of M(PPh 3 ) 4 or Pt(PEt 3 ) 4 with the respective dihaloaryl organics (Schemes 1 and 2) in toluene generates, via double oxidative addition of M(0), the bis( trans -M(PPh 3 ) 2 X)aryl complexes in good to excellent yield . These reactions can also be carried out in a benzene media; however, the yields are quite variable and generally diminished.…”

Section: Resultsmentioning

confidence: 99%

Preparation,viaDouble Oxidative Addition, and Characterization of Bimetallic Platinum and Palladium Complexes: Unique Building Blocks for Supramolecular Macrocycles.¹³C NMR Analysis of the Nature of the Palladium−Carbon Bond

et al. 1997

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The high-yield preparation, by double oxidative addition, of nine novel platinum and palladium bis(trans-M(PR3)2X)aryl (M = Pt or Pd; R = PPh3 or PEt3; X = Br or I; aryl = 1,4-benzene, 4,4‘-biphenyl, 4,4‘‘-ter-p-phenyl, 4,4‘-tolane, or 4,4‘-benzophenone) complexes from the reaction of Pt(PPh3)4, Pt(PEt3)4, or Pd(PPh3)4 with the respective dihalo aromatic in toluene is described. These complexes were fully characterized by elemental analysis, mass spectrometry, and NMR (1H, 13C{1H}, and 31P{1H}) and vibrational (IR or Raman) spectroscopies. The single-crystal molecular structure of 4,4‘-bis(trans-Pt(PEt3)2I)biphenyl (2a) was determined by X-ray crystallography. The key structural feature of this complex is the dihedral angle of 18.9° between the two planes defined by the phenyl groups of the biphenyl linkage. The nature of the palladium−carbon bond is investigated by 13C{1H} NMR spectroscopy; Taft's σR parameter is found to correlate in a linear fashion with [δ(C ipso ) − δ(C o )] for these palladium complexes. These data indicate the 13C chemical shift of C ipso is linearly related to the amount of π-electron density of the carbon bound to the palladium center. The potential utility of these bimetallic platinum and palladium complexes as subunits in the generation of organometallic macrocycles is described.

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Section: Resultsmentioning

confidence: 99%

Preparation,viaDouble Oxidative Addition, and Characterization of Bimetallic Platinum and Palladium Complexes: Unique Building Blocks for Supramolecular Macrocycles.¹³C NMR Analysis of the Nature of the Palladium−Carbon Bond

et al. 1997

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“…We have shown previously that 2-Me 3 SnC 6 F 4 PPh 2 is also a convenient alternative to 2-LiC 6 F 4 PPh 2 in the preparation of the digold(I) complex [Au 2 (μ-2-C 6 F 4 PPh 2 ) 2 ] . Following the pioneering work of Eaborn, Pidcock, et al, − (aryl)trimethyltin reagents have been used extensively for the selective transfer, under mild conditions, of one or two aryl groups to platinum(II), − but in the case of palladium(II) the reaction is usually successful only when, as in our case, the aryl groups bear a donor center. − …”

Section: Discussionmentioning

confidence: 99%

Bidentate Chelate Complexes of Palladium(II) with the Carbanion 2-C₆F₄PPh₂and Their Transformation into Complexes Containing Bridging 2-C₆F₄PPh₂

et al. 2011

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ARTICLEsolution by opening of the chelate rings to a tetranuclear complex of the same composition as 5, [Pd 4 (μ-Cl) 4 (μ-2-C 6 F 4 PPh 2 ) 4 ] (6), which is structurally analogous to 1. We now report the behavior of the corresponding bromide, iodide, carboxylate, pseudohalide, and acetylacetonato derivatives, thereby establishing the existence of a family of ortho-palladated compounds of a similar type, i.e., of identical composition but containing either chelate k 2 -P,C-2-C 6 F 4 PPh 2 or bridging μ 2 -P,C-2-C 6 F 4 PPh 2 . We have also discovered two compounds that display both coordination modes. Finally, we report reactions of 5 and 8 with acetonitrile and of 8 with PPh 3 and PCy 3 , which also lead to irreversible opening of the chelate ring.

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“…Construction of simple 1,4-arenediyl bridges between Pt(II) centers that are not stabilized by intramolecular coordination has been achieved via the transmetalation reaction of 1,4-bis(trimethylstannyl)benzene with dichloro(1,4-cyclooctadiene)platinum(II) and the oxidative addition of 1,4-diiodobenzene to tetrakis(triethylphosphine)platinum(0) . The synthesis of the diplatinum(IV) complex 9b using iodine(III) reagents opens a pathway to Pt(IV) complexes containing the archetypal 1,4-benzenediyl bridge.…”

Section: Discussionmentioning

confidence: 99%

Reactivity of Diaryliodine(III) Triflates toward Palladium(II) and Platinum(II): Reactions of C(sp²)−I Bonds to Form Arylmetal(IV) Complexes; Access to Dialkyl(aryl)metal(IV), 1,4-Benzenediyl-Bridged Platinum(IV), and Triphenylplatinum(IV) Species; and Structural Studies of Platinum(IV) Complexes

et al. 2004

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Diphenyliodine(III) triflate is able to transfer Ph + to Pd(II) and Pt(II) with cleavage of a phenyl-iodine bond and formation of metal(IV) species, leading to the first identified transfer of Ph + to Pd(II) from an aryl-halogen bond, and, for platinum, a methodology providing a facile route to dimethyl(aryl)platinum(IV) and 1,4-arenediyl-bridged Pt(IV) species and the first archetypal triarylplatinum(IV) complex. Thus, [IPh 2 ][OTf] reacts with PtMe 2 (bpy) (bpy ) 2,2′-bipyridine) at -50°C to form iodobenzene and the Pt(IV) complex trans-Pt IV (OTf)Me 2 -Ph(N∼N) (1b) (Ph trans to OTf), and on addition of NaI, the species PtIMe 2 Ph(bpy) (2a (Ph cis to I) and 2b (Ph trans to I) in 2:1 ratio) may be isolated at -20°C. Similarly, metalla-(II)cyclopentane complexes M(C 4 H 8 )(bpy) react with [IPh 2 ][OTf] to form trans-Pt(OTf)(C 4 H 8 )-Ph(bpy) (3b) and a 1:1 ratio of cis-(4a) and trans-Pd(OTf)(C 4 H 8 )Ph(bpy) (4b); addition of halide ion gives trans-PtI(C 4 H 8 )Ph(bpy) (5b) and a 1:3 ratio of cis and trans isomers for PdI(C 4 H 8 )Ph(bpy) (6a, 6b) and PdCl(C 4 H 8 )Ph(bpy) (7a, 7b). Complex 5b isomerizes to form a 2:1 mixture of cis-PtI(C 4 H 8 )Ph(bpy) (5a) and 5b at ambient temperature in acetone. Dimethyl(2,2′-bipyridine)palladium(II) reacts with [IPh 2 ][OTf] to form Pd(OTf)Me 2 Ph(bpy), followed by transfer of a methyl group from Pd(IV) to Pd(II), to form trimethylpalladium-(IV) species. Dimethyl(2,2′-bipyridine)platinum(II) reacts with [IPh(C 6 H 4 -4-I)][OTf], followed by addition of sodium iodide, to form a 1:1 mixture of trans-PtIMe 2 Ph(bpy) (2b) and transPtIMe 2 (C 6 H 4 -4-I)(bpy) (8b), and with [IPh(C 6 H 4 -4-IPh)][OTf] 2 to form the 1,4-arenediyl complex trans-1,4-{PtIMe 2 (bpy)} 2 C 6 H 4 (9b). Diphenyl{di(tert-butyl)-2,2′-bipyridine}platinum-(II) reacts with [IPh 2 ][OTf] at 25°C over 2 days to form the triphenylplatinum(IV) complex Pt(OTf)Ph 3 (Bu t 2 bpy) (10), and addition of iodide ion results in isolation of PtIPh 3 (Bu t 2 bpy) (11). Structural studies of trans-PtIMe 2 Ph(bpy) (2b) and trans-Pt(C 4 H 8 )Ph(bpy) (5b) reveal distorted octahedral geometry and the fac-PtC 3 configuration expected for all of the metal-(IV) complexes. The compound [IPh(C 6 H 4 -4-I)][OTf] has two sets of cation-anion pairs with a complex array of weak interactions, and the cations have C-I-C angles close to 90°.

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Synthese zweikerniger Platin‐Verbindungen mit 1,4‐Phenylen‐Brücke

Cited by 17 publications

References 6 publications

Preparation,viaDouble Oxidative Addition, and Characterization of Bimetallic Platinum and Palladium Complexes: Unique Building Blocks for Supramolecular Macrocycles.¹³C NMR Analysis of the Nature of the Palladium−Carbon Bond

Preparation,viaDouble Oxidative Addition, and Characterization of Bimetallic Platinum and Palladium Complexes: Unique Building Blocks for Supramolecular Macrocycles.¹³C NMR Analysis of the Nature of the Palladium−Carbon Bond

Bidentate Chelate Complexes of Palladium(II) with the Carbanion 2-C₆F₄PPh₂and Their Transformation into Complexes Containing Bridging 2-C₆F₄PPh₂

Reactivity of Diaryliodine(III) Triflates toward Palladium(II) and Platinum(II): Reactions of C(sp²)−I Bonds to Form Arylmetal(IV) Complexes; Access to Dialkyl(aryl)metal(IV), 1,4-Benzenediyl-Bridged Platinum(IV), and Triphenylplatinum(IV) Species; and Structural Studies of Platinum(IV) Complexes

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Synthese zweikerniger Platin‐Verbindungen mit 1,4‐Phenylen‐Brücke

Cited by 17 publications

References 6 publications

Preparation,viaDouble Oxidative Addition, and Characterization of Bimetallic Platinum and Palladium Complexes: Unique Building Blocks for Supramolecular Macrocycles.13C NMR Analysis of the Nature of the Palladium−Carbon Bond

Preparation,viaDouble Oxidative Addition, and Characterization of Bimetallic Platinum and Palladium Complexes: Unique Building Blocks for Supramolecular Macrocycles.13C NMR Analysis of the Nature of the Palladium−Carbon Bond

Bidentate Chelate Complexes of Palladium(II) with the Carbanion 2-C6F4PPh2and Their Transformation into Complexes Containing Bridging 2-C6F4PPh2

Reactivity of Diaryliodine(III) Triflates toward Palladium(II) and Platinum(II): Reactions of C(sp2)−I Bonds to Form Arylmetal(IV) Complexes; Access to Dialkyl(aryl)metal(IV), 1,4-Benzenediyl-Bridged Platinum(IV), and Triphenylplatinum(IV) Species; and Structural Studies of Platinum(IV) Complexes

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Preparation,viaDouble Oxidative Addition, and Characterization of Bimetallic Platinum and Palladium Complexes: Unique Building Blocks for Supramolecular Macrocycles.¹³C NMR Analysis of the Nature of the Palladium−Carbon Bond

Preparation,viaDouble Oxidative Addition, and Characterization of Bimetallic Platinum and Palladium Complexes: Unique Building Blocks for Supramolecular Macrocycles.¹³C NMR Analysis of the Nature of the Palladium−Carbon Bond

Bidentate Chelate Complexes of Palladium(II) with the Carbanion 2-C₆F₄PPh₂and Their Transformation into Complexes Containing Bridging 2-C₆F₄PPh₂