Water-soluble iridium and rhodium complexes with tris(hydroxymethyl)phosphine and their catalysis in biphasic hydrogenation and hydroformylation

Fukuoka, Atsushi; Kosugi, Wataru; Morishita, Fumiaki; Hirano, Masafumi; Komiya, Sanshiro; McCaffrey, Louise J.; Henderson, William

doi:10.1039/a808350i

Cited by 43 publications

(16 citation statements)

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“…Rhenium and technetium complexes of this ligand family have been shown to possess desirable attributes for use in radiopharmaceuticals. 2 Rh III , 3 Pd II , Pt II and Re V complexes 1c have been shown to be kinetically stabilised by such groups, and both rhodium 4 and ruthenium 5 compounds are active hydroformylation and hydrogenation catalysts, respectively. We have previously communicated 6 that the reaction of tris(hydroxymethyl)phosphine and ruthenium trichloride forms the all-trans complex [RuCl 2 -(P(CH 2 OH) 3 ) 2 (P(CH 2 OH) 2 H) 2 ] 1 with the highly unusual generation of two secondary phosphine groups on the metal.…”

Section: Introductionmentioning

confidence: 99%

Water-soluble hydroxyalkylated phosphines: examples of their differing behaviour toward ruthenium and rhodium

2004

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The reaction of P(CH2OH)3 (I) and P(C6H5)(CH2OH)2 (II) with RuCl3 in methanol eliminates two equivalents of formaldehyde to yield the mixed tertiary and secondary phosphine complexes all-trans-[RuCl2(P(CH2OH)3)2(P(CH2OH)2H)2] (1) and [RuCl2(P(C6H5)(CH2OH)2)2(P(C6H5)(CH2OH)H)2] (2), respectively. There is a high degree of hydrogen-bonding interactions between the hydroxymethyl groups in 1 and 2, although the phenyl groups of the latter reduce the extent of the network compared to 1. The generation of these mixed secondary and tertiary phosphine complexes is unprecedented. Under the same reaction conditions, the tris(hydroxypropyl)phosphine III formed no ruthenium complex. The reaction of P(CH2OH)3, P(C6H5)(CH2OH)2 and P{(CH2)3OH}3 with [RhCl(1,5-cod)]2 in an aqueous/dichloromethane biphasic medium yielded [RhH2(P(CH2OH)3)4]+ (3), [RhH2(P(C6H5)(CH2OH)2)4]+ (4) and [Rh(P(C6H5)(CH2OH)2)4]+ (5) and [Rh(P{(CH2)3OH}3)4]+ (6), respectively. Treating 5 with dihydrogen rapidly gave 4. The hydroxypropyl compound 6 formed the corresponding dihydride much more slowly in aqueous solution, although [RhH2(P{(CH2)3OH}3)4]+ (7) was readily formed by reaction with dihydrogen. Two separate reaction pathways are therefore involved; for P(CH2OH)3 and to a lesser extent P(C6H5)(CH2OH)2, the hydride source in the product is likely to be the aqueous solvent or the hydroxyl protons, whilst for P{(CH2)3OH}3 an oxidative addition of H2 is favoured. The protic nature of and was illustrated by the H-D exchange observed in d2-water. Dihydrides 3 and 4 reacted with carbon monoxide to yield the dicarbonyl cations [Rh(CO)2(P(CH2OH)3)3]+ (8) and [Rh(CO)2(P(C6H5)(CH2OH)2)3]+ (9). The analogous experiment with [RhH2(P{(CH2)3OH}3)4]+ resulted in phosphine exchange, although our experimental evidence points to the possibility of more than one fluxional process in solution.

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Section: Introductionmentioning

confidence: 99%

Water-soluble hydroxyalkylated phosphines: examples of their differing behaviour toward ruthenium and rhodium

2004

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“…[8] (Hydroxymethyl)phosphane ligands, especially the parent system P(CH 2 OH) 3 , have been employed to synthesize stable water-soluble complexes with catalytic active metals (e.g. Rh and Ir) [10] -for their use in biphasic catalysis [11] -or with cytotoxic transition metals such as Pt and Au [12] for potential medical application. In addition, hydroxymethylfunctionalized phosphanes deserve not only attention as versatile phosphane ligands but also as versatile candidates for crystal engineering studies.…”

Section: Introductionmentioning

confidence: 99%

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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“…Phos phines with hydroxyalkyl groups such as tris(hydroxymethyl)phosphine (P(CH 2 OH) 3 , THP), form stable water soluble complexes in the case of Pd, Pt, Rh, Re, Ru, Ir, and Mo [3][4][5][6][7][8]. However, few polynuclear complexes with THP and related hydro philic phosphines have been reported.…”

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confidence: 99%

Preparation and crystal structure of [Ru2(μ-Cl)3(P(CH2OH)3)6]Cl

Anyushin

Abramov

Kompankov

et al. 2015

Russ. J. Inorg. Chem.

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Water-soluble iridium and rhodium complexes with tris(hydroxymethyl)phosphine and their catalysis in biphasic hydrogenation and hydroformylation

Cited by 43 publications

References 10 publications

Water-soluble hydroxyalkylated phosphines: examples of their differing behaviour toward ruthenium and rhodium

Water-soluble hydroxyalkylated phosphines: examples of their differing behaviour toward ruthenium and rhodium

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

Preparation and crystal structure of [Ru2(μ-Cl)3(P(CH2OH)3)6]Cl

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