Supramolecular chemistry of half-sandwich organometallic building blocks based on RuCl2(p-cymene)Ph2PCH2Y

Dann, Sandra E.; Durran, Sean E.; Elsegood, Mark R. J.; Smith, Martin B.; Staniland, Paul M.; Talib, Salem; Dale, Sophie H.

doi:10.1016/j.jorganchem.2006.07.036

Cited by 31 publications

(23 citation statements)

References 56 publications

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“…Similar phenomena were described with [(η 6 -C 10 H 14 )RuCl 2 (L)] complexes having iso-nicotinic acid or 4-aminocinnamic acid [3] as well as Ph 2 CH 2 NHC 6 H 4 COOH [4] ligands.…”

Section: Introductionsupporting

confidence: 78%

“…As anions we used mono-sulfonated triphenylphosphine (mtppms, 1; well known from aqueous organometallic catalysis [8]) while the cation was Nbenzyl-1,3,5-triaza-7-phosphaadamantane, 2 (Scheme 1. 4 ] has been studied in hydrogenation of aldehydes [10] but this complex was found active also in hydrogenation of bicarbonate [11] and in hydration of nitriles [12]. These reactions are also catalyzed by the half-sandwich complexes formed in reactions of [(arene)RuCl 2 ] 2 and pta [13][14][15].…”

Section: Gulyás Et Al Obtained Bidentate Phosphorus Ligands Held Togementioning

confidence: 99%

“…The product was isolated as yellow powder and analysed by the same techniques used for identification of the product of the stepwise synthetic procedure; all parameters were found identical. [4] mentioned in the introduction was found to dimerize through intermolecular H-bonds between the carboxylic acid groups. Therefore the dimer necessarily consists of two monomeric half sandwich Ru-complexes having the same phosphine substitutents and consequently has a symmetric structure.…”

Section: Synthesis and Crystallographic Analysis Of (Pta-r)(mtppms) Smentioning

confidence: 99%

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Two in one: Charged tertiary phosphines held together by ionic or covalent interactions as bidentate phosphorus ligands for synthesis of half-sandwich Ru(II)-complexes

et al. 2013

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Ion pairs containing N-substituted derivatives of 1,3,5-triaza-7-phosphaadamantane (pta-R; R= benzyl, butyl, hexyl) as cations and monosulfonated triphenylphosphine (mtppms) as anion were synthetized and characterized (including X-ray diffraction, too). These ion pairs act as bidentate phosphorus ligands in reactions with [(η 6 -C 10 H 14 )RuCl 2 ] 2 , yielding mononuclear or dinuclear half sandwich Ru(II) complexes. A bisphosphine 3 of good watersolubility was synthesized in reaction of pta with 1,4-bis(chloromethyl)benzene and used for the synthesis of the water-soluble dinuclear complex [{(η 6 -C 10 H 14 )RuCl 2 } 2 (μ-3)]Cl 2 .

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“…Similar phenomena were described with [(η 6 -C 10 H 14 )RuCl 2 (L)] complexes having iso-nicotinic acid or 4-aminocinnamic acid [3] as well as Ph 2 CH 2 NHC 6 H 4 COOH [4] ligands.…”

Section: Introductionsupporting

confidence: 78%

Section: Gulyás Et Al Obtained Bidentate Phosphorus Ligands Held Togementioning

confidence: 99%

Section: Synthesis and Crystallographic Analysis Of (Pta-r)(mtppms) Smentioning

confidence: 99%

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Two in one: Charged tertiary phosphines held together by ionic or covalent interactions as bidentate phosphorus ligands for synthesis of half-sandwich Ru(II)-complexes

et al. 2013

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“…We, and others, have found that ditertiary phosphanes such as those of general formula (R 2 PCH 2 ) 2 N(R) have interesting coordination properties [7,8] including their use in selfassembly reactions through covalent bonds or H-bonding contacts. [2][3][4][5]9] The tetraphenyl-substituted phosphane (Ph 2 PCH 2 ) 2 N(R), closely related to the three-carbon spacer (Ph 2 PCH 2 ) 2 CH 2 [1,3-bis(diphenylphosphanyl)propane, dppp], has been widely utilised in several metal-catalysed reactions. [10][11][12] Phosphaadamantane ligands containing one or more trioxa-or carbon-only-based cages have been shown to eral drops of CH 3 2 Cl 2 have been elucidated by single-crystal X-ray crystallography.…”

Section: Introductionmentioning

confidence: 99%

“…[2][3][4][5]9] The tetraphenyl-substituted phosphane (Ph 2 PCH 2 ) 2 N(R), closely related to the three-carbon spacer (Ph 2 PCH 2 ) 2 CH 2 [1,3-bis(diphenylphosphanyl)propane, dppp], has been widely utilised in several metal-catalysed reactions. [10][11][12] Phosphaadamantane ligands containing one or more trioxa-or carbon-only-based cages have been shown to eral drops of CH 3 2 Cl 2 have been elucidated by single-crystal X-ray crystallography. The X-ray structures of 10·CH 2 Cl 2 · 0.5C 4 H 10 O and 13·2CH 2 Cl 2 demonstrate how nonsymmetric ditertiary phosphane complexes bearing one pendant phosphaadamantane moiety can be used as metalloligands in the controlled syntheses of novel bi-and trimetallic complexes.…”

Section: Introductionmentioning

confidence: 99%

Coordination Studies of a New Nonsymmetric Ditertiary Phosphane Bearing a Single Phosphaadamantane Cage

et al. 2008

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The new nonsymmetric ditertiary phosphane, Ph2P(CH2)2PAd (1), was prepared in one‐step from Ph2PCH=CH2 andH‐PAd (H‐PAd = 1,3,5,7‐tetramethyl‐2,4,8‐trioxa‐6‐phosphaadamantane) by a hydrophosphination reaction using 2,2′‐azo‐bisisobutyronitrile (AIBN) as free radical initiator. The sterically encumbered phosphaadamantane cage in 1 was found to influence the coordination capabilities of this ligand. The reaction of 1 with [PdCl2(cod)] or [Pt(CH3)2(cod)] (cod = cycloocta‐1,5‐diene) gave the corresponding κ2‐P,P′‐chelate complexes cis‐[PdCl2(1)] (2) and cis‐[Pt(CH3)2(1)] (3), respectively. The dinuclear gold(I) complex [Ph2P(AuCl)(CH2)2PAd(AuCl)] (4) was prepared from 1 and 2 equiv. of [AuCl(tht)] (tht = tetrahydrothiophene). In contrast, the cleavage of the chloro‐bridged dimers {RuCl2(η6‐p‐cymene)}2 or {MCl2(η5‐Cp*)}2 (M = Rh, Ir) with 1 gave the κ1‐P‐monodentate complexes [RuCl2(η6‐p‐cymene)(1)] (5), [RhCl2(η5‐Cp*)(1)] (6) and [IrCl2(η5‐Cp*)(1)] (7), respectively, in which the ‐PAd group is non‐coordinating. Chloride abstraction from 6 (or 7) can be accomplished upon addition of Na[SbF6] to generate the cationic κ2‐P,P′‐chelate complexes 8b (and 9b). Alternatively 8a (or 9a) could be observed, as their chloride salts, by 31P{1H} NMR spectroscopy upon addition of several drops of CH3OH to CDCl3 solutions of 6 (or 7). The reaction of 5–7 with [AuCl(tht)] gave the dinuclear complexes [κ2‐P,P′‐μ‐RuCl2(η6‐p‐cymene){Ph2P(CH2)2PAd(AuCl)}] (10), [κ2‐P,P′‐μ‐RhCl2(η5‐Cp*){Ph2P(CH2)2PAd(AuCl)}] (11) and [κ2‐P,P′‐μ‐IrCl2(η5‐Cp*){Ph2P(CH2)2PAd(AuCl)}] (12). Reaction of two equiv. of 5 with the labile precursors [PdCl2(CH3CN)2] or [PtCl2(PhCN)2] gave instead the novel trinuclear Ru2Pd and Ru2Pt complexes trans‐[{κ2‐P,P′‐μ‐RuCl2(η6‐p‐cymene){Ph2P(CH2)2PAd}}2PdCl2] (13) and trans‐[{κ2‐P,P′‐μ‐RuCl2(η6‐p‐cymene){Ph2P(CH2)2PAd}}2PtCl2] (14), respectively. All new compounds have been fully characterised by spectroscopic and analytical methods. Furthermore the structures of 3·CHCl3, 4, 5, 7·CHCl3, 10·CH2Cl2·0.5C2H10O and 13·2CH2Cl2 have been elucidated by single‐crystal X‐ray crystallography. The X‐ray structures of 10·CH2Cl2·0.5C4H10O and 13·2CH2Cl2 demonstrate how nonsymmetric ditertiary phosphane complexes bearing one pendant phosphaadamantane moiety can be used as metalloligands in the controlled syntheses of novel bi‐ and trimetallic complexes.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Mononuclear and Heterodinuclear Metal Complexes of Nonsymmetric Ditertiary Phosphanes Derived from R₂PCH₂OH

et al. 2007

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The new nonsymmetric ditertiary phosphanes, Ph 2 PCH 2 N-(R)CH 2 PAd [3a: R = C 6 H 5 , 3b: R = C 6 H 4 (4-CH 3 )] were prepared using a three-step sequence of condensation reactions. Hence treatment of AdP-H (AdP-H = 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phosphaadamantane) with (CH 2 O) n at 110°C gave the adamantane-derived hydroxymethylphosphane 1, which upon condensation with C 6 H 5 NH 2 or C 6 H 4 (4-CH 3 )-NH 2 gave the secondary aminophosphanes HN(R)CH 2 PAd [2a: R = C 6 H 5 , 2b: R = C 6 H 4 (4-CH 3 )]. Further condensation of 2a or 2b with Ph 2 PCH 2 OH gave 3a or 3b in high yields

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Supramolecular chemistry of half-sandwich organometallic building blocks based on RuCl2(p-cymene)Ph2PCH2Y

Cited by 31 publications

References 56 publications

Two in one: Charged tertiary phosphines held together by ionic or covalent interactions as bidentate phosphorus ligands for synthesis of half-sandwich Ru(II)-complexes

Two in one: Charged tertiary phosphines held together by ionic or covalent interactions as bidentate phosphorus ligands for synthesis of half-sandwich Ru(II)-complexes

Coordination Studies of a New Nonsymmetric Ditertiary Phosphane Bearing a Single Phosphaadamantane Cage

Mononuclear and Heterodinuclear Metal Complexes of Nonsymmetric Ditertiary Phosphanes Derived from R₂PCH₂OH

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Supramolecular chemistry of half-sandwich organometallic building blocks based on RuCl2(p-cymene)Ph2PCH2Y

Cited by 31 publications

References 56 publications

Two in one: Charged tertiary phosphines held together by ionic or covalent interactions as bidentate phosphorus ligands for synthesis of half-sandwich Ru(II)-complexes

Two in one: Charged tertiary phosphines held together by ionic or covalent interactions as bidentate phosphorus ligands for synthesis of half-sandwich Ru(II)-complexes

Coordination Studies of a New Nonsymmetric Ditertiary Phosphane Bearing a Single Phosphaadamantane Cage

Mononuclear and Heterodinuclear Metal Complexes of Nonsymmetric Ditertiary Phosphanes Derived from R2PCH2OH

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Mononuclear and Heterodinuclear Metal Complexes of Nonsymmetric Ditertiary Phosphanes Derived from R₂PCH₂OH