Chemistry in environmentally benign media Part 1. Synthesis and characterization of 1,2-bis[bis(hydroxymethyl)phosphino]ethane (‘HMPE’). X-ray structure of [Pt{(HOH2C)2PCH2CH2P(CH2OH)2}2](Cl)2

Reddy, V. Sreenivasa; Katti, Kattesh V.; Barnes, Charles L.

doi:10.1016/0020-1693(95)04555-4

Cited by 36 publications

(35 citation statements)

References 19 publications

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“…19,20 In sharp contrast, the simple (hydroxymethyl)bisphosphines 1 and 2 produced transition metal complexes with similar metals in 1:2 metal-to-ligand stoichiometry. 14,15 The reaction of P 2 S 2 -COOH, 12, with ReO 2 (py) 4 Cl (py ) pyridine) to produce a water-soluble and kinetically inert Re V complex 29 is of particular significance because of its potential applications in nuclear medicine (Scheme 13). 26 This reaction presents prospects of using radiometals of diagnostic (e.g., 99m Tc, γ emitter) and therapeutic (e.g., 186/188 Re, emitter) importance to produce radiolabeled bifunctional chelates.…”

Section: Methodsmentioning

confidence: 99%

“…14,15 Early reports on the formylation of 1,2-bis(phosphino)ethane and related analogues used harsh reaction conditions that involved employing high temperatures (>80°C) and longer durations under sealed setups. 16 It is important to recognize that phosphorus(III) hydrides are toxic and pyrophoric.…”

Section: Synthesis and Formylation Of Multinuclear Phosphinesmentioning

confidence: 99%

“…In fact, our laboratory, for the first time, demonstrated that formylation reaction of 1,2-bis(phosphino)benzene or -ethane (Scheme 2) can be carried out (using 37% formaldehyde) in ethanol in unsealed glass wares, at 25°C or lower, to produce the corresponding hydroxymethylated 1,2-bis(bis(hydroxymethyl)phosphino)benzene, 1, or -ethane, 2, respectively, in excellent yields. 14,15 We quickly tested the efficacy of this new formylating strategy on the tri-and tetranuclear phosphorus(III) hydrides developed recently in our laboratory (Schemes 3 and 4). 17,18 The formylation of these multinuclear P III hydrides occurred readily in diethyl ether, even at 0°C, to produce a new and interesting class of water-soluble triphosphine, 3, and tetraphosphine, 4, functionalized with hydroxymethyl units on the P III centers.…”

Section: Synthesis and Formylation Of Multinuclear Phosphinesmentioning

confidence: 99%

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Design and Development of Functionalized Water-Soluble Phosphines: Catalytic and Biomedical Implications

et al. 1998

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Water is an environmentally (and biologically) benign solvent, and therefore, development of chemistry in aqueous media has long been a desirable goal for chemists. In particular, chemistry of water-soluble transition metal compounds has gained considerable prominence in recent years because of their usefulness in biphasic (aqueous-organic) catalysis 1 and biomedicine. 2 High solubility of transition metal compounds in water becomes a primary requirement in the design and development of catalysts for use under biphasic media because of the need for efficient separation and recovery of expensive transition metal catalysts (in aqueous media) from organic products. Additionally, the ability of specific transition metals to exert therapeutic (and diagnostic) influence on certain diseases has provided increased impetus in the development of new water-soluble and in vivo-stable transition metal compounds. 2,3 Of the various ligands available to stabilize specific oxidation states of transition metals and to produce aqueous soluble coordination compounds, functionalized phosphines are the most attractive class of ligands because of their versatile coordination chemistry. While aqueous soluble di-or trisulfonated arylphosphines, such as P(m-C 6 H 4 SO 3 Na) 3 , have largely been employed in the development of highly active water-soluble transition metal catalysts, 1 hydrophilic alkylphosphines are being highly sought after in order to gain specific structure-activity advantages in both catalytic and biomedical applications. In this context, the formylation of PH 3 , first reported by Hoffman et al., to produce tetrakis(hydroxymethyl)phosphonium chloride (THPC) has provided one of the earliest examples for the synthesis of hydrophilic alkylphosphines (Scheme 1). 4 Water-soluble tris(hydroxymethyl)phosphine (THP) was produced upon reaction of THPC with a suitable base (e.g., triethylamine or sodium bicarbonate buffer) (Scheme 1). 5 The transition metal chemistry of THP and other functionalized phosphines, over the years, has enabled the development of a wide spectrum of water-soluble transition metal/organometallic compounds for potential use in biphasic catalysis 5,6 and biomedicine. 7,8 The ease of transformation of P-H bonds into P-C bonds (as outlined in Scheme 1) is, undoubtedly, a synthetic novelty and the (hydroxymethyl)phosphorus compounds have provided a diverse range of chemical, catalytic, biological, environmental, and biomedical applications. 5-10 Despite the potential academic interest and scope for further technological advances, formylation reactions of functionalized phosphorus hydrides and, especially, of multinuclear phosphorus hydrides (i.e., bis-, tris-, or tetraphosphines) have, surprisingly, remained largely unexplored.It must be recognized that PH 3 , in its pure form, is an extremely hazardous chemical compound. It ignites in air at about 150°C and decomposes to produce phosphoric acid. 11 In its impure form, PH 3 gas is spontaneously inflammable at room temperature and this insta-

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Section: Methodsmentioning

confidence: 99%

Section: Synthesis and Formylation Of Multinuclear Phosphinesmentioning

confidence: 99%

Section: Synthesis and Formylation Of Multinuclear Phosphinesmentioning

confidence: 99%

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Design and Development of Functionalized Water-Soluble Phosphines: Catalytic and Biomedical Implications

et al. 1998

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“…The ease with which P-H bonds in primary phosphines can be converted to P-C bonds, as shown in Schemes 9 and 10, demonstrates the importance of primary phosphines in the design and development of novel organophosphorus compounds. In particular, functionalized hydroxymethyl phosphines have become ubiquitous in the development of watersoluble transition metal/organometallic compounds for potential applications in biphasic aqueous-organic catalysis and also in transition metal based pharmaceutical development [53][54][55][56][57][58][59][60][61][62]. Extensive investigations on the coordination chemistry of hydroxymethyl phosphines have demonstrated unique stereospecific and kinetic propensity of this class of water-soluble phosphines [53][54][55][56][57][58][59][60][61][62].…”

Section: Formylation Reactions Of Primary Phosphinesmentioning

confidence: 99%

“…Representative examples outlined in Fig. 4, depict bidentate and multidentate coordination modes and the unique kinetic propensity to stabilize various oxidation states of metal centers, such as Re(V), Rh(III), Pt(II) and Au(I), in aqueous media [53][54][55][56][57][58][59][60][61][62]. Therefore, the importance of functionalized primary phosphines in the development of multidentate water-soluble phosphines cannot be overemphasized.…”

Section: Formylation Reactions Of Primary Phosphinesmentioning

confidence: 99%

New Vistas in Chemistry and Applications of Primary Phosphines

Katti¹,

Pillarsetty²,

Kannan³

2003

New Aspects in Phosphorus Chemistry III

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Primary phosphines (R-PH 2 ) are an important class of compounds in organophosphorus chemistry. Although discovered over a century ago, their chemistry and applications have gained prominence in recent years. This review discusses recent developments on synthesis, molecular structure, properties, and applications of primary phosphines. In particular, discussions on synthesis and properties emphasize recent results from our laboratory on the chemical architecture of amide, thioether, and carboxylate functionalized primary bisphosphines. The utility of bromo-and aminopropyl phosphines (X(CH 2 ) 3 PH 2 ; X=Br or NH 2 ) as building blocks to produce 'designer' primary phosphines that display exceptional oxidative stability is described. The review also discusses the utility of carboxylate functionalized primary phosphines for incorporation on to peptides and their potential applications in catalysis and biomedicine.

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Synthese des ersten Biokonjugats aus einem chelatisierenden Bisphosphan und einem Peptid ausgehend von einem neuartigen funktionalisierten Phosphor(III)-hydrid-Synthon

et al. 1999

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Eine bemerkenswerte Oxidationsbeständigkeit zeichnet das Carboxy‐funktionalisierte primäre Bisphosphan 1 aus. Es kann über die COOH‐Gruppe mit Biomolekülen zu Konjugaten verknüpft werden, ohne daß die PH2‐Gruppen vorher geschützt werden müssen. Ein neuartiges, wasserlösliches Bisphosphan wurde durch die Reaktion der PH2‐Gruppen von 1 mit Formaldehyd unter milden Bedingungen erhalten.

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Chemistry in environmentally benign media Part 1. Synthesis and characterization of 1,2-bis[bis(hydroxymethyl)phosphino]ethane (‘HMPE’). X-ray structure of [Pt{(HOH2C)2PCH2CH2P(CH2OH)2}2](Cl)2

Cited by 36 publications

References 19 publications

Design and Development of Functionalized Water-Soluble Phosphines: Catalytic and Biomedical Implications

Design and Development of Functionalized Water-Soluble Phosphines: Catalytic and Biomedical Implications

New Vistas in Chemistry and Applications of Primary Phosphines

Synthese des ersten Biokonjugats aus einem chelatisierenden Bisphosphan und einem Peptid ausgehend von einem neuartigen funktionalisierten Phosphor(III)-hydrid-Synthon

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