Phosphorus Ligands

Downing, Joanne H.; Smith, Martin B.

doi:10.1016/b0-08-043748-6/01049-5

Cited by 29 publications

(24 citation statements)

References 465 publications

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“…In methanol, the ligand undergoes selective cleavage of a methylene carbon-phosphorus bond, with concomitant formation of a phosphinite ligand, Me 2 POMe. Given the relative inertness of tertiary alkyl phosphanes in other contexts (e.g., such compounds do not undergo alkali metal induced cleavage, [14] in contrast to aryl phosphanes or mixed aryl/alkyl phosphanes), the observed reactivity is all the more remarkable. The reaction product is an organometallic complex with a direct FeÀC bond or an agostic Fe-H-C interaction, depending on the reaction temperature and the nature of the counterion.…”

Section: Resultsmentioning

confidence: 99%

Ligand Cleavage Put into Reverse: PC Bond Breaking and Remaking in an Alkylphosphane Iron Complex

Kohl¹,

Heinemann²,

Hummert³

et al. 2006

Chemistry A European J

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Complex formation between FeX(2)6 H(2)O (X=BF(4) or ClO(4)) and the pyridine-derived tetrapodal tetraphosphane C(5)H(3)N[CMe(CH(2)PMe(2))(2)](2) (1) in methanol proceeds with solvent-induced cleavage of one PMe(2) group. Depending on the reaction temperature and the nature of the counterion, iron(II) is coordinated, in distorted square-pyramidal fashion, by the anionic remainder of the chelating ligand, C(5)H(3)N[CMe(CH(2)PMe(2))(2)][CMe(CH(2)PMe(2))(CH(2) (-))] (NP(3)C(-) donor set: X=BF(4), -50 degrees C: 2; X=ClO(4), RT: 4) or its protonated form C(5)H(3)N[CMe(CH(2)PMe(2))(2)][CMe(CH(2)PMe(2))(CH(3))], in which the methyl group is in agostic interaction with the metal centre (X=BF(4), RT: 3; X=ClO(4), +50 degrees C: 5). A monodentate phosphinite ligand Me(2)POMe, formed from the cleaved PMe(2) group and methanol, completes the coordination octahedron in both cases. Working in CD(3)OD (X=BF(4), RT) gives the deuterium-substituted analogue of 3, with ligands L(CH(2)D) (L=residual chelating ligand) and Me(2)POCD(3). A mechanism for the observed phosphorus-carbon bond cleavage is suggested. Complex 2, when isolated at -50 degrees C, is stable in the solid state even at room temperature. The reaction of 2 in methanol with carbon monoxide (10.5 bar) at elevated temperature forms, in addition to as yet unidentified side products, the carbonyl complex [(1)Fe(CO)](BF(4))(2) (7), in which the previous P--C bond cleavage has been reversed, reforming the original tetrapodal pentadentate NP(4) ligand 1. All compounds have been fully characterised, including X-ray structure analyses in most cases.

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Section: Resultsmentioning

confidence: 99%

Ligand Cleavage Put into Reverse: PC Bond Breaking and Remaking in an Alkylphosphane Iron Complex

Kohl¹,

Heinemann²,

Hummert³

et al. 2006

Chemistry A European J

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“…[26] The new ligand Ph 2 P(CH 2 ) 2 PAd (1) was prepared in a single-step, by a AIBN free radical initiated hydrophosphination reaction of H-PAd (H-PAd = 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phosphaadamantane) with Ph 2 PCH=CH 2 and could be obtained in high yield (ca. 80 %) as a transparent colourless oil [Equation (1)].…”

Section: Ligand Synthesismentioning

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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“…[12][13][14] Furthermore, a related C 3 backbone diphosphane structurally comparable to dppp, is the bulky CH 3 ), 5c: Pd, R = C 6 H 5 , 5d: Pd, R = C 6 H 4 (4-CH 3 )]. In contrast, bridge cleavage of the dimers {RuCl 2 (η 6 -p-cym)} 2 or {IrCl 2 (η 5 -Cp*)} 2 with 3a gave the κ 1 -P-monodentate complexes RuCl 2 (η 6 -p-cym)(3a) (6) and IrCl 2 (η 5 -Cp*)(3a) (7), respectively, in which the -PAd group is noncoordinating.…”

Section: Introductionmentioning

confidence: 99%

“…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 …”

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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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Phosphorus Ligands

Cited by 29 publications

References 465 publications

Ligand Cleavage Put into Reverse: PC Bond Breaking and Remaking in an Alkylphosphane Iron Complex

Ligand Cleavage Put into Reverse: PC Bond Breaking and Remaking in an Alkylphosphane Iron Complex

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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Phosphorus Ligands

Cited by 29 publications

References 465 publications

Ligand Cleavage Put into Reverse: PC Bond Breaking and Remaking in an Alkylphosphane Iron Complex

Ligand Cleavage Put into Reverse: PC Bond Breaking and Remaking in an Alkylphosphane Iron Complex

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