31P and 13C NMR of Transition Metal Phosphine Complexes

Pregosin, Paul S.; Kunz, Roland W.

doi:10.1007/978-3-642-48830-6

Cited by 364 publications

(240 citation statements)

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“…The latter is therefore slightly more shielded by the presence of the trans thioether, consistent with previous observation that a ligand of greater trans influence shifts a 3 1~ resonance to higher field (10).…”

Section: Nuclear Magnetic Resonance Studiessupporting

confidence: 91%

“…Using phosphines as coligands, we have been able to make platinum(I1) complexes with R = Me, L = PPh3 (3), PPh2Me (4), PPhMe2 (S), or PMe3 (6); R = Ph, L = PPh3 (7), PPh2Me (8), or PPhMe2 (9). Palladium(I1) phosphino complexes were more difficult to prepare, and were restricted to that with L = PPh3, R = Me (10). Neutral type 2 complexes have been prepared for both Pt (11) and Pd (12).…”

Section: Introductionmentioning

confidence: 99%

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Complexes of hybrid ligands. Some Pd²⁺ and Pt²⁺ complexes of fluoro-alkoxy thioether ligands; the measurement of the trans-effect of phosphines on thioether inversion

Boeré¹,

Willis²

1986

Can. J. Chem.

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. J. Chem. 64,492 (1986).The hybrid ligands R-S-CH2-C(CF3)2-O-(R = CH3 or C6H5) have been used in conjunction with the other donors to prepare complexes of pt2+ and pd2+. Five-membered chelate rings are formed by coordination through the hard alkoxy and the soft thioether donor sites. Products are of two types: neutral MCI{RSCH2C(CF3)20)(PR3) or cationic [ M { R S C H~C ( C F~)~O ) ( P R~)~+ , and their geometry is assigned. Variable temperature nmr measurements are used to follow the inversion of the thioether function in the hybrid chelate ring, and values of AGS are calculated. From a comparison of the barrier to inversion in various complexes, the dynamic trans effect of various ligands is assessed including, for the first time using this criterion, the trialkylphosphines. IntroductionIn the first part of this series (2), we described the synthesis of molecules of general formula RSCH2C(CF3)20H, containing both a fluorinated alcohol and a thioether function. In the mono-ionized form, these may act as bidentate, chelating, ligands toward transition metal ions. The combination of the hard -C(CF3)20-donor with the soft thioether function enables them to form stable complexes with the softer transition metal ions, and we have described studies on the neutral bis-complexes M[RSCH2C(CF3)20]2, which show cis geometry for M = Pt and both cis and trans for M = Pd.In the present paper, we describe the extension of this study to the preparation of two additional types of complexes of these hybrid ligands, cationic complexes of type 1 with alkyl-and arylphosphine as coligand, and neutral type 2 complexes with phosphine and chloride as coligands.

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Section: Nuclear Magnetic Resonance Studiessupporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Complexes of hybrid ligands. Some Pd²⁺ and Pt²⁺ complexes of fluoro-alkoxy thioether ligands; the measurement of the trans-effect of phosphines on thioether inversion

Boeré¹,

Willis²

1986

Can. J. Chem.

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“…The coordination-induced shift of the phosphorus signal (d( 31 P) coord ±d( 31 P) non-coord ) is between 26 and 41 ppm to lower field. These values and the magnitudes of the 1 J(Pt, P) coupling constants (3075± 3501 Hz) are as expected [8]. As for other acylplatinum complexes trans-[Pt(COR)Cl(L) 2 ] (L = phosphine) [9], the C±O stretching vibrations in the IR spectra are at 1636 (2 a) and 1649 cm ±1 (2 d) and the Pt±Cl stretching vibrations are at 265 (2 a) and 260 cm ±1 (2 d).…”

Section: Spectroscopic Characterizationsupporting

confidence: 52%

“…The phosphorus resonances were found at 32.2 ppm (3 a) and 43.7 ppm (3 b). In both cases the signals are shifted to low field in comparison with the phosphorus resonance of the free dadpe ligand (d = ±12.5), as expected when five-membered rings are formed [8]. The 1 H and 13 C NMR spectra of 3 a fully support the identity of the complex.…”

Section: Spectroscopic Characterizationmentioning

confidence: 52%

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On the Reactivity of Platina-β-diketones - Synthesis and Characterization of Acylplatinum(II) Complexes

Steinborn

Hoffmann

Gerisch

et al. 2000

Z. anorg. allg. Chem.

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The platina‐β‐diketones [Pt2{(COR)2H}2(μ‐Cl)2] (1, R = Me a, Et b) react with phosphines L in a molar ratio of 1 : 4 through cleavage of acetaldehyde to give acylplatinum(II) complexes trans‐[Pt(COR)Cl(L)2] (2) (R/L = Me/P(p‐FC6H4)3 a, Me/P(p‐CH2=CHC6H4)Ph2 b, Me/P(n‐Bu)3 c, Et/P(p‐MeOC6H4)3 d). 1 a reacts with Ph2As(CH2)2PPh2 (dadpe) in a molar ratio of 1 : 2 through cleavage of acetaldehyde yielding [Pt(COMe)Cl(dadpe)] (3 a) (configuration index: SP‐4‐4) and [Pt(COMe)Cl(dadpe)] (configuration index: SP‐4‐2) (3 b) in a ratio of about 9 : 1. All acyl complexes were characterized by 1H, 13C and 31P NMR spectroscopy. The molecular structures of 2 a and 3 a were determined by single‐crystal X‐ray diffraction. The geometries at the platinum centers are close to square planar. In both complexes the plane of the acyl ligand is nearly perpendicular to the plane of the complex (88(2)° 2 a, 81.2(5)° 3 a).

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Complexation Studies with a Calix[4]arene-Derived Phosphinite − Divergent Arrays of Cavities Linked by MCl2 Fragments (M = Pd, Pt)

Faidherbe¹,

Wieser²,

Matt³

et al. 1998

Eur. J. Inorg. Chem.

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A cone‐shaped calix[4]arene‐derived monophosphinite, 25,27‐di(ethoxycarbonylmethoxy)‐26‐hydroxy‐28‐(diphenylphosphinooxy)calix[4]arene (L1), has been prepared in two steps from calix[4]arene. Treatment of L1 with [AuCl(tetrahydrothiophene)] in tetrahydrofuran gave the phosphinite complex [AuClL1] (1). Reaction of [PdCl2(PhCN)2] with two equivalents of L1 gave selectively trans‐[PdCl2L12] (2). Complex 2 · 2 CH2Cl2 crystallizes in the triclinic space group P1¯. The molecule is centrosymmetric, leading to a divergent array of the two calixarene moieties. The palladium atom resides outside both cones. As a result of steric interactions, the meta and para carbon atoms of the PPh2‐bearing aryl ring are significantly pushed to the interior of the cavity. The related platinum complex trans‐[PtCl2L122] (3), was obtained similarly from [PtCl2(PhCN)2] and presents in the solid state a structure which is isomorphous to that of 2. The diphosphinite 25,27‐di(ethoxycarbonylmethoxy)‐26,28‐bis(diphenylphosphinoxy)calix[4]arene (cone) (L2) has also been prepared and reacts with [PtCl2(PhCN)2] to yield oligomeric material.

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31P and 13C NMR of Transition Metal Phosphine Complexes

Cited by 364 publications

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Complexes of hybrid ligands. Some Pd²⁺ and Pt²⁺ complexes of fluoro-alkoxy thioether ligands; the measurement of the trans-effect of phosphines on thioether inversion

Complexes of hybrid ligands. Some Pd²⁺ and Pt²⁺ complexes of fluoro-alkoxy thioether ligands; the measurement of the trans-effect of phosphines on thioether inversion

On the Reactivity of Platina-β-diketones - Synthesis and Characterization of Acylplatinum(II) Complexes

Complexation Studies with a Calix[4]arene-Derived Phosphinite − Divergent Arrays of Cavities Linked by MCl2 Fragments (M = Pd, Pt)

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31P and 13C NMR of Transition Metal Phosphine Complexes

Cited by 364 publications

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Complexes of hybrid ligands. Some Pd2+ and Pt2+ complexes of fluoro-alkoxy thioether ligands; the measurement of the trans-effect of phosphines on thioether inversion

Complexes of hybrid ligands. Some Pd2+ and Pt2+ complexes of fluoro-alkoxy thioether ligands; the measurement of the trans-effect of phosphines on thioether inversion

On the Reactivity of Platina-β-diketones - Synthesis and Characterization of Acylplatinum(II) Complexes

Complexation Studies with a Calix[4]arene-Derived Phosphinite − Divergent Arrays of Cavities Linked by MCl2 Fragments (M = Pd, Pt)

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Complexes of hybrid ligands. Some Pd²⁺ and Pt²⁺ complexes of fluoro-alkoxy thioether ligands; the measurement of the trans-effect of phosphines on thioether inversion

Complexes of hybrid ligands. Some Pd²⁺ and Pt²⁺ complexes of fluoro-alkoxy thioether ligands; the measurement of the trans-effect of phosphines on thioether inversion