The Use of 1,3,5-Triaza-7-Phosphaadamantane (PTA), A Water-Soluble , Air Stable Ligand, in Organometallic Chemistry and Catalysis

Darensbourg, Donald J.; Decuir, Tara J.; Reibenspies, Joseph H.

doi:10.1007/978-94-011-0355-8_6

Cited by 18 publications

(10 citation statements)

References 36 publications

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“…The (N)C-N distances of the PTA ligands are found to be 1.49 Å, consistent with nonprotonated PTA ligands. 15 Two equivalents of water cocrystallize with 1 and are found in a channel formed by the packing of 1. The solid-state structure of 2 was determined by X-ray crystallography.…”

Section: Resultsmentioning

confidence: 99%

“…9 PTA has been used to make a variety of water-soluble metal complexes, which have shown moderate to good activity for a range of catalytic reactions. [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25] Bullock reported the first PTA-substituted half-sandwich metallocene metal hydride complex CpW(CO) 2 PTA(H); however, this complex was found to be insoluble in water. 26 Dyson has reported the synthe-Organometallics 2004, 23 sis, characterization, and reactivity of a series of [(η 6 arene)Ru(PTA) 2 X] + and (η 6 -arene)Ru(PTA)X 2 complexes, where X ) Cl, Br, I, NCS and arene ) C 6 H 6 , cymene.…”

Section: Introductionmentioning

confidence: 99%

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Aqueous Organometallic Chemistry: Synthesis, Structure, and Reactivity of the Water-Soluble Metal Hydride CpRu(PTA)₂H

Frost

Mebi

2004

Organometallics

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The reaction of CpRu(PTA)2Cl (1) with KOH in methanol afforded the water-soluble hydride CpRu(PTA)2H (2) in good yield. The solid-state structures of both CpRu(PTA)2H and the previously reported CpRu(PTA)2Cl are described and exhibit classic piano stool geometries. Complex 2 is one of a very few structurally characterized CpRu(PR3)2H compounds known and the only one that is water-soluble. The ruthenium hydride is stable and soluble (S 25 ° C = 20 mg/mL) in deoxygenated water; however, the complex does react with chlorinated solvents to yield 1. Complex 2 undergoes H/D exchange with D2O, and the kinetics of this process were monitored by 31P NMR spectroscopy as a function of temperature. Activation parameters for the reaction of 2 with D2O were obtained: ΔH ⧧ = 68 ± 2 kJ/mol; ΔS ⧧ = −94 ± 7 J/mol·K. A normal kinetic isotope effect of 7.9 was calculated for the H/D exchange reaction described here. These kinetic parameters suggest an associative mechanism with little Ru−H (or Ru−D) bond cleavage at the transition state. The reaction is postulated to occur via protonation of the hydride ligand of 2 by water followed by deprotonation by the resultant hydroxide. Finally DFT calculations were performed on all complexes and are consistent with the observed solid-state structures of 1 and 2.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Aqueous Organometallic Chemistry: Synthesis, Structure, and Reactivity of the Water-Soluble Metal Hydride CpRu(PTA)₂H

Frost

Mebi

2004

Organometallics

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“…81 This could be achieved using ligands that could help solubilise the metal complexes. 81 This could be achieved using ligands that could help solubilise the metal complexes.…”

Section: Trans-palladium Complexes As Anti-cancer Agentsmentioning

confidence: 99%

“…The water solubility of organometallic complexes is an important criterion that has found far-reaching applications in synthesis and biological sciences. 81 This could be achieved using ligands that could help solubilise the metal complexes. 1,3,5-Triaza-7-phosphaadmantane (PTA) 82 is one such readily available and air-stable ligand that has proved to be a versatile and electron-rich phosphine ligand and has found varied applications.…”

Section: Trans-palladium Complexes As Anti-cancer Agentsmentioning

confidence: 99%

Anti-cancer palladium complexes: a focus on PdX₂L₂, palladacycles and related complexes

2014

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Much success has been achieved with platinum-based chemotherapeutic agents, i.e. through interactions with DNA. The long-term application of Pt complexes is thwarted by issues, leading scientists to examine other metals such as palladium which could exhibit complementary modes of action (given emphasis wherever known). Over the last 10 years several research groups have focused on the application of an eclectic array of palladium complexes (of the type PdX2L2, palladacycles and related structures) as potential anti-cancer agents. This review therefore provides readers with an up to date account of the advances that have taken place over the past several decades.

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“…Furthermore, the metal ion can present some geometrical preferences, thus imparting selective binding tendencies towards anions of a given shape. [9] Therefore, the displacement of the receptor-bound pyrocatechol violet by a phosphate anion would be communicated visually as well as spectrophotometrically. [7] These reports led us to explore the metal complex of H-bpmp as a receptor for phosphate ions.…”

Section: Naked-eye Detection Of Phosphate Ions Inmentioning

confidence: 99%

Methyl Transfer from Rhenium to Coordinated Thiolate Groups

Shan

Ellern

Espenson

2002

Angew. Chem. Int. Ed.

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A prominent reaction of vitamin B 12 is the conversion of d,l-homocystein, HS(CH 2 ) 2 CHNH 2 CO 2 H, to l-methionine, MeS(CH 2 ) 2 CHNH 2 CO 2 H, with methylcobalamin and methylcobinamide. [1±4] Methyl bis(dimethylglyoximato)cobalt(iii) and related complexes also convert thiols to thioethers [Eq. (1)]: [5] There are, however, a lack of precedents in the literature for similar conversions that do not involve organocobalt complexes. In this work, new reactions of rhenium complexes have been examined, and sound evidence for the analogous conversion has now been obtained.With 1,2-ethanedithiol (edtH 2 ), however, a quite different result was obtained. As Re VII was reduced to Re V , one edtH 2 molecule was transformed to HS(CH 2 ) 2 SMe, which remains coordinated to the rhenium(v) center through both sulfur atoms in a k 2 fashion [Eq. (3)]:Details of the synthesis and characterization of the dark-red complex 1 are given in the Experimental Section. A similar reaction starting with [MeReO(edt)(PPh 3 )] (3) [7] gave the same product in lower yield. Crystals of 1 suitable for X-ray diffraction could not be obtained. We have formulated the composition of 1 to be [ReO(k 2 -edt)(k 2 -edtMe)] based on elemental analysis and spectroscopic data. An alternative formulation as an organorhenium(vii) compound, [Me-ReO(edt) 2 ], could not be ruled out by these data. However, the evidence is in favor of structure 1 as the CH 3 resonance appears at d ¼ 1.90 ppm, which is further downfield than would be expected for a methyl group coordinated to a Re VII center. Indeed, the proposed mechanism suggests that [MeReO(edt) 2 ] lies on the pathway to 1.Chemical methods were therefore used to obtain information about the molecular structure of 1, particularly with respect to whether the MeÀRe interaction present in the starting material is retained. The reaction of 1 with H 2 O 2 in wet acetonitrile gave ReO 4 À ions, which are easily recognized from the characteristic UV spectrum. The same product was obtained from 5, another compound that lacks a MeÀRe bond. In contrast, several compounds that do contain a Me À Re bond (2, 3, and 4) cleanly reacted with H 2 O 2 to form COMMUNICATIONS

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The Use of 1,3,5-Triaza-7-Phosphaadamantane (PTA), A Water-Soluble , Air Stable Ligand, in Organometallic Chemistry and Catalysis

Cited by 18 publications

References 36 publications

Aqueous Organometallic Chemistry: Synthesis, Structure, and Reactivity of the Water-Soluble Metal Hydride CpRu(PTA)₂H

Aqueous Organometallic Chemistry: Synthesis, Structure, and Reactivity of the Water-Soluble Metal Hydride CpRu(PTA)₂H

Anti-cancer palladium complexes: a focus on PdX₂L₂, palladacycles and related complexes

Methyl Transfer from Rhenium to Coordinated Thiolate Groups

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The Use of 1,3,5-Triaza-7-Phosphaadamantane (PTA), A Water-Soluble , Air Stable Ligand, in Organometallic Chemistry and Catalysis

Cited by 18 publications

References 36 publications

Aqueous Organometallic Chemistry: Synthesis, Structure, and Reactivity of the Water-Soluble Metal Hydride CpRu(PTA)2H

Aqueous Organometallic Chemistry: Synthesis, Structure, and Reactivity of the Water-Soluble Metal Hydride CpRu(PTA)2H

Anti-cancer palladium complexes: a focus on PdX2L2, palladacycles and related complexes

Methyl Transfer from Rhenium to Coordinated Thiolate Groups

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Aqueous Organometallic Chemistry: Synthesis, Structure, and Reactivity of the Water-Soluble Metal Hydride CpRu(PTA)₂H

Aqueous Organometallic Chemistry: Synthesis, Structure, and Reactivity of the Water-Soluble Metal Hydride CpRu(PTA)₂H

Anti-cancer palladium complexes: a focus on PdX₂L₂, palladacycles and related complexes