New pyridyl modified phosphines: Synthesis and late transition-metal coordination studies

Durran, Sean E.; Smith, Martin B.; Dale, Sophie H.; Coles, Simon J.; Hursthouse, Michael B.; Light, Mark E.

doi:10.1016/j.ica.2005.12.068

Cited by 26 publications

(11 citation statements)

References 59 publications

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“…Coordination numbers from 3 to 5 are seen in the silver(I) compounds, while the copper(I) complexes are 4-and 5-coordinate. This versatility in coordination gives rise to several distorted geometries such as T-shaped (4), tetrahedral (3, 5, 7, and 8), capped tetrahedral (5), and trigonal bipyramidal (4). The different coordination modes reported for the compounds of 1 are affected by the counterion's extent of interaction with the metal center.…”

Section: Synthesismentioning

confidence: 99%

“…A wide variety of ligands containing a pyridyl functionality in conjuction with phosphorus in the form of phosphanes, phosphinites, phosphonites, phosphates and phosphazoles have been synthesized and studied. [1][2][3][4] Complexes synthesized with these ligands have exhibited catalytic [1,[5][6][7] and luminescence properties, as well as being useful in the construction of extended structures. [8][9][10][11] We have mainly been interested in synthesizing pyridylcontaining phosphinites and phosphonites where the pyridyl is attached at either the 3-or 4-position which precludes the formation of discrete chelating structures.…”

Section: Introductionmentioning

confidence: 99%

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The Variable Binding Modes of Phenylbis(pyrid‐2‐ylmethyl)phosphane and Bis(pyrid‐2‐ylmethyl) Phenylphosphonite with Ag^I and Cu^I

2009

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A series of new bridging phosphane and phosphonite structures forming three‐ and six‐membered rings with the metal centers were synthesized and characterized. The resulting compounds of phenylbis(pyrid‐2‐ylmethyl)phosphane (1) with the silver(I) salts of trifluoroacetate (tfa–), tetrafluoroborate (BF4–), and trifluoromethanesulfonate (OTf–), and copper tetrakis(acetonitrile) hexafluorophosphate (PF6–) shows the flexibility of the ligand by displaying different coordination modes associated with the electronic and structural characteristics of the corresponding anion. Accordingly, ligand 1 in these complexes displays two different binding modes. With Agtfa and AgBF4 compounds 3 and 4 are obtained where the ligand chelates to two silver atoms that exhibit normalAg–Ag contacts in the range of 2.9 Å. When AgOTf or Cu(NCCH3)4PF6 are used, one molecule of 1 bridges the metal centers through a phosphorus atom while another is terminally bound. This induces short M–M distances of 2.6871 and 2.568 Å for 5 and 6, respectively. Similarly, the coordination behavior of the heterofunctional bis(pyrid‐2‐ylmethyl) phenylphosphonite ligand (2) is reported with Cu(NCCH3)4PF6 (7) and AgBF4 (8) to form two novel discrete molecules. In these complexes 2 coordinates through the P and N atoms, with the difference that in 7 the O atom of one of the carbinol arms is also bound to the Cu. Elemental analysis, variable‐temperature multinuclear NMR spectroscopy, single‐crystal X‐ray diffraction, and low‐temperature luminescence studies were carried out to fully characterize the compounds. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Section: Synthesismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The Variable Binding Modes of Phenylbis(pyrid‐2‐ylmethyl)phosphane and Bis(pyrid‐2‐ylmethyl) Phenylphosphonite with Ag^I and Cu^I

2009

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“…[1][2][3][4][5] We have found that by using two consecutive Mannich based condensation reactions, nonsymmetric ditertiary phosphanes such as 3a and 3b can be realised. Accordingly, insertion of paraformaldehyde into the P-H bond of AdP-H (1:1 ratio) at 110°C for 90 min affords the hydroxymethyl-functionalised phosphane 1.…”

Section: Ligand Synthesesmentioning

confidence: 99%

“…As part of ongoing studies [1][2][3][4][5] in our group we have been interested in developing new tertiary and symmetric ditertiary phosphanes using Mannich-based condensation reactions. Compounds of the formula (R 2 PCH 2 ) 2 N(R) and {(R 2 PCH 2 ) 2 N} 2 (R) are two such examples [6][7][8][9][10] which have interesting coordination properties, catalytic applications and, more recently, are important ligands for self-assembly reactions using covalent bonds or H-bonding interactions.…”

Section: Introductionmentioning

confidence: 99%

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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“…As part of continuing studies [1][2][3][4][5][6] in our group we are interested in developing new tertiary and symmetric ditertiary phosphane ligands using simple condensation reactions. 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.…”

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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New pyridyl modified phosphines: Synthesis and late transition-metal coordination studies

Cited by 26 publications

References 59 publications

The Variable Binding Modes of Phenylbis(pyrid‐2‐ylmethyl)phosphane and Bis(pyrid‐2‐ylmethyl) Phenylphosphonite with Ag^I and Cu^I

The Variable Binding Modes of Phenylbis(pyrid‐2‐ylmethyl)phosphane and Bis(pyrid‐2‐ylmethyl) Phenylphosphonite with Ag^I and Cu^I

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

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

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New pyridyl modified phosphines: Synthesis and late transition-metal coordination studies

Cited by 26 publications

References 59 publications

The Variable Binding Modes of Phenylbis(pyrid‐2‐ylmethyl)phosphane and Bis(pyrid‐2‐ylmethyl) Phenylphosphonite with AgI and CuI

The Variable Binding Modes of Phenylbis(pyrid‐2‐ylmethyl)phosphane and Bis(pyrid‐2‐ylmethyl) Phenylphosphonite with AgI and CuI

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

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

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The Variable Binding Modes of Phenylbis(pyrid‐2‐ylmethyl)phosphane and Bis(pyrid‐2‐ylmethyl) Phenylphosphonite with Ag^I and Cu^I

The Variable Binding Modes of Phenylbis(pyrid‐2‐ylmethyl)phosphane and Bis(pyrid‐2‐ylmethyl) Phenylphosphonite with Ag^I and Cu^I

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