Water-soluble tris(hydroxymethyl)phosphine complexes with nickel, palladium, and platinum. Crystal structure of [Pd{P(CH2OH)3}4].cntdot.CH3

Ellis, James W.; Harrison, Karl N.; Hoye, Peter A. T.; Orpen, A. Guy; Pringle, Paul G.; Smith, Martin B.

doi:10.1021/ic00040a009

Cited by 177 publications

(78 citation statements)

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“…Thus, the molecular structure of 3 is similar to that of the first atropisomeric pyrylium salt we recently reported. [6] Pyrylium salt 3 was further converted into the corresponding racemic phosphinine 1 by treatment with excess PA C H T U N G T R E N N U N G (CH 2 OH) 3 [11] in pyridine at reflux (Scheme 2). After column chromatography, compound 1 was obtained as a yellow powder (34 % yield) and could be isolated as yellow needles after recrystallization from hot acetonitrile or pentane.…”

Section: Resultsmentioning

confidence: 99%

Developing a New Class of Axial Chiral Phosphorus Ligands: Preparation and Characterization of Enantiopure Atropisomeric Phosphinines

Müller

Pidko

Staring

et al. 2008

Chemistry A European J

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Both enantiomers of the first atropisomeric phosphinine (1) have been isolated by using analytical HPLC on a chiral stationary phase. The enrichment of one enantiomer and a subsequent investigation into its racemization kinetics revealed a barrier for internal rotation of DeltaG(298)(double dagger) = (109.5+/-0.5) kJ mol(-1), which is in excellent agreement with the theoretically predicted value of DeltaG(298)(double dagger) =116 kJ mol(-1). Further analysis with UV and circular dichroism spectroscopies and density functional theory calculations led to the determination and assignment of the absolute configurations of both enantiomers. These results are the basis for future investigations into this new class of axially chiral phosphinine-based ligands and their possible applications in asymmetric homogeneous catalysis.

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Section: Resultsmentioning

confidence: 99%

Developing a New Class of Axial Chiral Phosphorus Ligands: Preparation and Characterization of Enantiopure Atropisomeric Phosphinines

Müller

Pidko

Staring

et al. 2008

Chemistry A European J

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“…Since the first platinum complexes of the type [PtClR(cod)] (cod = 1,5-cyclooctadiene) were reported by Clark and Manzer (I), they have served as excellent precursors to a range of organoplatinum species, including bis(phosphine) (2) or diphosphine (3) compounds, or dppm-bridged A-frames (4). [PdC12(cod)] with a slight excess of tetrabenzyltin for 7.5 h, followed by purification, ave the product as a yellow solid in good yield.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of the complexes [PdCIR(cod)] (R = benzyl, ethyl; cod = 1,5-cyclooctadiene). β-Elimination from [PdCIEt(cod)] to give the η¹,η² and η³ isomers of [Pd₂(μ-Cl)₂(C₈H₁₃)₂]

Stockland¹,

Anderson²,

Rath³

et al. 1996

Can. J. Chem.

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Treatment of [PdCl,(cod)] with tetrabenzyltin gives the benzylpalladium complex [PdCI(CH,Ph)(cod)] (cod = 1.5-cyclooctadiene). la, whose structure has been determined by X-ray crystallography. It adopts approximate square-planar geometry, with the double bonds perpendicular to the square plane. The corresponding ethylpalladium derivative l b has been prepared by a similar-method, but it is considerably less stable. It decomposes by p-elimination to produce ethene and a transient Key words: palladium, diene complexes, allyl complexes, isomerization, p-elimination.RCsurnC : Le traitement du [PdCl,(cod)] avec le tCtrabenzylCtain conduit au complexe benzylpalladium [PdCI(CH,Ph)(cod)] (cod = cycloocta-l,5-dikne), la, dont on a dCterminC la structure par diffraction des rayons X. I1 adopte une gComCtrie plan carrC dans laquelle les doubles liaisons sont perpendiculaires au plan carre. On a prCparC le dCrivC Cthylpalladium correspondant, lb, par une mCthode semblable; il est toutefois beaucoup moins stable. I1 se dCcompose par une Climination P pour former de I'Cthkne et un hydrure complexe transitoire qui peut donner lieu soit B une insertion migratoire conduisant au [Pd,(p-CI),(q1,q2-C,H,,),], 2a, soit h une Climination reductrice dinucleaire avec une deuxikme molCcule de l b qui fournit de I'Cthane, du [PdCl,(cod)], du cyclooctadikne libre et du palladium mCtallique. On a aussi prCparC le complexe 2a par rkaction du [PdCl,(cod)] avec le NaBH,. A des tempkratures plus ClevCes, le composC 2a se transforme en un mClange B I'Cquilibre avec I'isomkre q3-allyle 2b. On a aussi CtudiC les rCactions du [PdCl,(cod)] ou du K,PdCI, en solution aqueuse, en prCsence de cyclooctadikne, qui conduisent aux produits 2a ou 2b.

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“…The resulting 1 J Pt,P coupling constant of 3490 Hz clearly indicates that the platinum atom has the cis-configuration. [21] This is evident by the fact that the corresponding trans-isomers of similar Pt complexes exhibit 1 J Pt,P = 2162 Hz). [21] This trend can be simplified explained by the higher trans-influence of phosphorus compared to halide ligands, which weakens a Pt-P bond and hence lowers the Pt,P coupling constant.…”

Section: Resultsmentioning

confidence: 95%

“…[21] This is evident by the fact that the corresponding trans-isomers of similar Pt complexes exhibit 1 J Pt,P = 2162 Hz). [21] This trend can be simplified explained by the higher trans-influence of phosphorus compared to halide ligands, which weakens a Pt-P bond and hence lowers the Pt,P coupling constant. The 31 P NMR spectrum of complex 5 in CD 3 OD shows one resonance signal at δ = 15.8 ppm for the two equivalent phosphorus nuclei.…”

Section: Resultsmentioning

confidence: 95%

Cyclohexylbis(hydroxymethyl)phosphane: A Hydrophilic Phosphane Capable of Forming Novel Hydrogen‐Bonding Networks

2006

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The cyclohexyl‐substituted (hydroxymethyl)phosphane CyP(CH2OH)2 (1) has been prepared by reaction of the corresponding primary phosphane CyPH2 with aqueous formaldehyde. Compound 1 has been used as building block for the synthesis of new functionalized water‐soluble phosphorus compounds. Thus, Mannich‐type condensation of 1 with excess glycine affords the air‐stable amino acid phosphane conjugate CyP[CH2N(H)CH2COOH]2 (2). Simple oxidation of 1 with hydrogen peroxide and elemental sulfur leads to the crystalline chalcogenide derivatives CyP(O)(CH2OH)2 (3) and CyP(S)(CH2OH)2 (4). X‐ray diffraction analyses of the latter revealed distinct intermolecular hydrogen bonding motifs and possess different types of hydrogen bond networks to each other due to the different proton acceptor ability of the chalcogen atom X of the P=X group (X = O, S): while the oxygen atom of the P=O moiety in 3 serves as proton acceptor, affording a P=O–HO bifurcated network, the sulfur atom of the P=S group denies hydrogen bonding interactions. In addition, the ligand ability of 1 has been studied towards Pt(+2) and Cu(+1) ions: Reaction of 1 with Pt(COD)Cl2 (COD = cycloocta‐1,5‐diene) furnishes the air‐stable complex cis‐[PtCl2{CyP(CH2OH)2}2] (5), while the crystalline dimeric Cu(+1) complex [CuI{CyP(CH2OH)2}2]2 (6) results from the reaction of CuI with two molar equivalents of 1. The complex 6 shows a intermolecular hydrogen bonding pattern different from that of 1, 3 and 4, respectively. The new coordination compounds 5 and 6 represent metal‐phosphane labelled alcohols which are promising building blocks for the synthesis of metal‐based drugs. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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Water-soluble tris(hydroxymethyl)phosphine complexes with nickel, palladium, and platinum. Crystal structure of [Pd{P(CH2OH)3}4].cntdot.CH3

Cited by 177 publications

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Developing a New Class of Axial Chiral Phosphorus Ligands: Preparation and Characterization of Enantiopure Atropisomeric Phosphinines

Developing a New Class of Axial Chiral Phosphorus Ligands: Preparation and Characterization of Enantiopure Atropisomeric Phosphinines

Synthesis of the complexes [PdCIR(cod)] (R = benzyl, ethyl; cod = 1,5-cyclooctadiene). β-Elimination from [PdCIEt(cod)] to give the η¹,η² and η³ isomers of [Pd₂(μ-Cl)₂(C₈H₁₃)₂]

Cyclohexylbis(hydroxymethyl)phosphane: A Hydrophilic Phosphane Capable of Forming Novel Hydrogen‐Bonding Networks

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Water-soluble tris(hydroxymethyl)phosphine complexes with nickel, palladium, and platinum. Crystal structure of [Pd{P(CH2OH)3}4].cntdot.CH3

Cited by 177 publications

References 0 publications

Developing a New Class of Axial Chiral Phosphorus Ligands: Preparation and Characterization of Enantiopure Atropisomeric Phosphinines

Developing a New Class of Axial Chiral Phosphorus Ligands: Preparation and Characterization of Enantiopure Atropisomeric Phosphinines

Synthesis of the complexes [PdCIR(cod)] (R = benzyl, ethyl; cod = 1,5-cyclooctadiene). β-Elimination from [PdCIEt(cod)] to give the η1,η2 and η3 isomers of [Pd2(μ-Cl)2(C8H13)2]

Cyclohexylbis(hydroxymethyl)phosphane: A Hydrophilic Phosphane Capable of Forming Novel Hydrogen‐Bonding Networks

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Synthesis of the complexes [PdCIR(cod)] (R = benzyl, ethyl; cod = 1,5-cyclooctadiene). β-Elimination from [PdCIEt(cod)] to give the η¹,η² and η³ isomers of [Pd₂(μ-Cl)₂(C₈H₁₃)₂]