Paramagnetic Phosphametallocenes

Burney, Claire; Carmichael, Duncan; Forissier, Kareen; Green, J. C.; Mathey, François; Ricard, Louis; Wendicke, S.

doi:10.1080/10426500213308

Cited by 6 publications

(2 citation statements)

References 3 publications

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“…We have recently had some success in using the 2,5-di-tertbutylphospholyl ligand 5 [1] to prepare a variety of unusual diamagnetic phosphametallocenes 6-8 [1,2] and the first stable monophosphacobaltocene 9, [3] and were interested to employ the same ligand in an attempt to generate and understand an example of the still-unknown class of paramagnetic phosphanickelocenes. [9][10][11] A number of previous studies could potentially have given rise to phosphanickelocenes. The earliest, employing heavily substituted di-and triphospholide anions, gave diamagnetic mononuclear 18ve ring-slipped sandwich complexes 10 [12] and 11.…”

Section: Introductionmentioning

confidence: 98%

Synthesis and Properties of [NiCp*(2,5‐tBu₂PC₄H₂)], a 20‐Valence‐Electron Phosphanickelocene

Burney

Carmichael

Forissier

et al. 2005

Chemistry A European J

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The reaction of the bulky phospholide salt Li(2,5-tBu2PC4H2) x 2THF (1; THF = tetrahydrofuran) with [NiCp*(acac)] (HCp* = pentamethylcyclopentadiene, Hacac = acetylacetone) gives the green air-sensitive phosphanickelocene [NiCp*(2,5-tBu2PC4H2)] (2) in yields of about 85%. An X-ray structural determination of 2 shows long Ni-ring bonds and "delocalised" ring P-C and C-C bonds characteristic of a classical 20-valence-electron (ve) nickelocene. The electronic structure of 2 has been clarified through a combined Amsterdam density functional (ADF) and photoelectron spectroscopic study, which indicates that the higher lying semi-occupied molecular orbital (SOMO) (-5.82 eV) has a' symmetry and that the phosphorus "lone pair" is energetically low-lying (-8.15 eV). Oxidation of phosphanickelocene 2 by AgBF4 occurs quantitatively to give the corresponding air-sensitive orange phosphanickelocenium salt [NiCp*(2,5-tBu2PC4H2)][BF4] (3). This complex has also been characterised by an X-ray crystallographic study, which reveals long Ni-C(alpha) and short C(alpha)-C(beta) bonds in the phospholyl ligand indicative of a SOMO having a'' symmetry. PMe3 reacts with 2 at room temperature to provoke a ring-slip reaction that gives the 18ve complex [NiCp*eta1-(2,5-tBu2PC4H2)(PMe3)] (4), but shows no reaction with the phosphanickelocenium salt 3 under the same conditions.

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Section: Introductionmentioning

confidence: 98%

Synthesis and Properties of [NiCp*(2,5‐tBu₂PC₄H₂)], a 20‐Valence‐Electron Phosphanickelocene

Burney

Carmichael

Forissier

et al. 2005

Chemistry A European J

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“…Our studies of phosphametallocenes built around late transition metals (2 M = Ru, 9 Co, 10 Co + , 11 Rh + , 11 Ir + , 11 Ni, 12 Ni +12 ) suggest that the substitution of ruthenium for iron will generate novel complexes showing improved stability. 13 However, synthesising complexes of type 2 has always involved the use of highly encumbered phospholyl ligands which promote the formation of the desired h 5 -complexes by exerting steric pressure upon the otherwise kinetically-favoured dimers (e.g.…”

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confidence: 94%

Synthesis and resolution of the planar chirality of ester-functionalised phospharuthenocenes

et al. 2004

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A Self‐Assembling Ligand Switch That Involves Hydroxide Addition to an sp² Hybridised Phosphorus Atom – A System Allowing OH^– Mediated Uptake of [MCl₂] (M = Pd, Pt) Centres

et al. 2019

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The coordination chemistry of the 1,1′-diphosphacobaltocenium salt [Co(η 5 -2-TBS-3,4-Me 2 -PC 4 H) 2 ] + BF 4 -(rac-1) and its derivatives with respect to [MCl 2 ] (M = Pd, Pt) centres is presented. Rac-1, showing two sp 2 hybridised phosphorus atoms and a positive charge, is stable towards strong electrophiles (PhCH 2 Br, MeI), but undergoes attack by hydroxide at phosphorus with subsequent rearrangement to form the neutral conjugate base [Co{η 5 -(2-TBS-3,4-Me 2 -PC 4 H)}{η 4 -(1-O,1-H-2-TBS-3,4-Me 2 -PC 4 H)}] (rac-2). Rac-1 undergoes reaction with [MCl 2 (PhCN) 2 ] (M=Pd, Pt) in damp chloroform to form the P sp2 -P sp3 chelating sec-phosphinite complexes [MCl 2 {Co{η 5 -(2-TBS-[a]

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Paramagnetic Phosphametallocenes

Cited by 6 publications

References 3 publications

Synthesis and Properties of [NiCp*(2,5‐tBu₂PC₄H₂)], a 20‐Valence‐Electron Phosphanickelocene

Synthesis and Properties of [NiCp*(2,5‐tBu₂PC₄H₂)], a 20‐Valence‐Electron Phosphanickelocene

Synthesis and resolution of the planar chirality of ester-functionalised phospharuthenocenes

A Self‐Assembling Ligand Switch That Involves Hydroxide Addition to an sp² Hybridised Phosphorus Atom – A System Allowing OH^– Mediated Uptake of [MCl₂] (M = Pd, Pt) Centres

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Paramagnetic Phosphametallocenes

Cited by 6 publications

References 3 publications

Synthesis and Properties of [NiCp*(2,5‐tBu2PC4H2)], a 20‐Valence‐Electron Phosphanickelocene

Synthesis and Properties of [NiCp*(2,5‐tBu2PC4H2)], a 20‐Valence‐Electron Phosphanickelocene

Synthesis and resolution of the planar chirality of ester-functionalised phospharuthenocenes

A Self‐Assembling Ligand Switch That Involves Hydroxide Addition to an sp2 Hybridised Phosphorus Atom – A System Allowing OH– Mediated Uptake of [MCl2] (M = Pd, Pt) Centres

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Synthesis and Properties of [NiCp*(2,5‐tBu₂PC₄H₂)], a 20‐Valence‐Electron Phosphanickelocene

Synthesis and Properties of [NiCp*(2,5‐tBu₂PC₄H₂)], a 20‐Valence‐Electron Phosphanickelocene

A Self‐Assembling Ligand Switch That Involves Hydroxide Addition to an sp² Hybridised Phosphorus Atom – A System Allowing OH^– Mediated Uptake of [MCl₂] (M = Pd, Pt) Centres