Synthesis of Anionic Iron Polyphosphides by Reaction of White Phosphorus with “Cp*Fe<sup>−</sup>”

Schnöckelborg, Eva‐Maria; Weigand, Jan J.; Wolf, Robert

doi:10.1002/anie.201101038

Cited by 41 publications

(36 citation statements)

References 49 publications

(30 reference statements)

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“…It is worth noting that late transition metal arene complexes have also been used for P4 activation recently (Schnöckelborg et al, 2011).…”

Section: P 4 Activation By Scandium Arene Complexesmentioning

confidence: 99%

“…Sc 3 P 7 was the first example of a Zintl-type P7 3-compound formed directly from P4 activation without using an alkali metal or its equivalent as reducing agents Charles et al, 1996;Fritz et al, 1990;Scheer et al, 2010;Schnöckelborg et al, 2011). Three types of phosphorous atoms were found to be present in Sc 3 P 7 : Papex, Pedge, and Pbottom.…”

Section: Figure 14mentioning

confidence: 99%

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Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Huang

Diaconescu

2014

Including Actinides

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Rare earth chemistry has witnessed remarkable advances in recent years. In particular, ancillary ligands other than cyclopentadienyl derivatives have been introduced to the organometallic chemistry and their complexes exhibit distinct reactivity and properties compared to the metallocene or half-sandwiched analogues. The present chapter reviews arene-bridged rare earth complexes with an emphasis on those compounds obtained by reduction reactions. A particular emphasis is placed on rare earth complexes supported by 1,1′-ferrocenediyl diamides since they show the most diverse chemistry with arenes: fused arenes, such as naphthalene and anthracene, formed inverse-sandwiched complexes, in which the arene is dianionic; weakly conjugated arenes, such as biphenyl, p-terphenyl, and 1,3,5-triphenylbenzene, were unexpectedly reduced by four electrons and led to 6-carbon, 10- electron aromatic systems; on the contrary, (E)-stilbene, which has a carbon-carbon double bond between the two phenyl rings, could only be reduced by two electrons, which were located on the carbon-carbon double bond instead of the phenyl rings.

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“…It is worth noting that late transition metal arene complexes have also been used for P4 activation recently (Schnöckelborg et al, 2011).…”

Section: P 4 Activation By Scandium Arene Complexesmentioning

confidence: 99%

Section: Figure 14mentioning

confidence: 99%

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Huang

Diaconescu

2014

Including Actinides

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“…Ellis and co‐workers prepared the intriguing sandwich complex B (Figure ) by treating [Ti(C 10 H 8 ) 3 ] 2− (C 10 H 8 =naphthalene) with P 4 . We investigated the reactivity of the naphthalene ferrate [Cp*Fe(C 10 H 8 )] − with P 4 . A mixture of several structurally diverse products was formed, including the crystallographically characterized complexes C and D (Figure ).…”

Section: Introductionmentioning

confidence: 99%

“… Anionic transition metal polyphosphido complexes directly obtained by P 4 activation. Cp*=C 5 Me 5 , Dipp=2,6‐ i Pr 2 C 6 H 3 …”

Section: Introductionmentioning

confidence: 99%

Selective P₄ Activation by a Highly Reduced Cobaltate: Synthesis of Dicobalt Tetraphosphido Complexes

Pelties

Maier

Herrmann

et al. 2016

Chemistry A European J

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Although the chemistry of transition metal polyphosphide anions has attracted significant attention, there are few reports of studies in which such species have been synthesized directly from white phosphorus. [K(OEt ) {Co(BIAN)(cod)}] (1, BIAN=1,2-bis(2,6-diisopropylphenylimino)acenaphthene, cod=1,5-cyclooctadiene), which is readily prepared by ligand exchange from [K(thf) {Co(cod) }], reacts with P to afford [{K(thf)} {(BIAN)Co} (μ-η :η -P )] (2 a) in 61 % yield (isolated product). [{K(OEt )} {(BIAN)Co} (μ-η :η -P )] (2 b) and [K([18]crown-6)(MeCN)] [{(BIAN)Co} (μ-η :η -P )] (2 c) were obtained by recrystallizing 2 a from diethyl ether and acetonitrile (and using [18]crown-6 in case of 2 c). Oxidation of 2 a with [Cp Fe]BAr (one equivalent) and subsequent recrystallization of the product from different solvents gave [K(OEt ){(BIAN)Co} (μ-η :η -P )] (3 a) and [K(dme) ][{(BIAN)Co} (μ-η :η -P )] (3 b; dme=1,2-dimethoxyethane). Neutral [{(BIAN)Co} (μ-η :η -P )] (4) was obtained in moderate yield by oxidizing 2 a with two equivalents of [Cp Fe]BAr . The new complexes were characterized by NMR, EPR (in the case of 3 a), and UV/Vis spectroscopy, and elemental analysis. The molecular structures revealed by X-ray crystallography display planar cyclic or open-chain P units sandwiched between {(BIAN)Co} fragments.

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“…In 2002, Ellis and co-workersprovided the first insights by reacting P 4 with an aphthalene-stabilized titanate that afforded the all-inorganic metallocene [(h 5 -P 5 ) 2 Ti] 2À (A;S cheme 1). [12] Later,W olf and co-workersdescribed the formation of iron polyphosphides B and C through P 4 -aggregation induced by anionic [Cp*Fe(h 4 -C 10 H 8 )] À (Cp* = C 5 (CH 3 ) 5 ), [13] and recently the preparation of dinuclearc obalt tetraphosphido complex D by reaction of P 4 with [Co(BIAN)(cod)] À (BIAN = 1,2-bis(2,6-diisopropylphenylimino)-acenaphthene, cod = 1,5-cyclooctadiene). [14] The group of Ruiz reported the fragmentation of P 4 into P 2 (E), facilitated by the triply bonded molybdenate [Mo 2 Cp 2 (m-PCy 2 )(m-CO) 2 ] À (Cp = C 5 H 5 ).…”

mentioning

confidence: 99%

Metalate‐Mediated Functionalization of P₄ by Trapping Anionic [Cp*Fe(CO)₂(η¹‐P₄)]⁻ with Lewis Acids

et al. 2017

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The development of selective functionalization strategies of white phosphorus (P4) is important to avoid the current chlorinated intermediates. The use of transition metals (TMs) could lead to catalytic procedures, but these are severely hampered by the high reactivity and unpredictable nature of the tetrahedron. Herein, we report selective first steps by reacting P4 with a metal anion [Cp*Fe(CO)2]− (Cp*=C5(CH3)5), which, in the presence of bulky Lewis acids (LA; B(C6F5)3 or BPh3), leads to unique TM‐substituted LA‐stabilized bicyclo[1.1.0]tetraphosphabutanide anions [Cp*Fe(CO)2(η1‐P4⋅LA)]−. Their P‐nucleophilic site can be subsequently protonated to afford the transient LA‐free neutral butterflies exo,endo‐ and exo,exo‐Cp*Fe‐ (CO)2(η1‐P4H), allowing controllable stepwise metalate‐mediated functionalization of P4.

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Synthesis of Anionic Iron Polyphosphides by Reaction of White Phosphorus with “Cp*Fe⁻”

Cited by 41 publications

References 49 publications

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Selective P₄ Activation by a Highly Reduced Cobaltate: Synthesis of Dicobalt Tetraphosphido Complexes

Metalate‐Mediated Functionalization of P₄ by Trapping Anionic [Cp*Fe(CO)₂(η¹‐P₄)]⁻ with Lewis Acids

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Synthesis of Anionic Iron Polyphosphides by Reaction of White Phosphorus with “Cp*Fe−”

Cited by 41 publications

References 49 publications

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Selective P4 Activation by a Highly Reduced Cobaltate: Synthesis of Dicobalt Tetraphosphido Complexes

Metalate‐Mediated Functionalization of P4 by Trapping Anionic [Cp*Fe(CO)2(η1‐P4)]− with Lewis Acids

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Synthesis of Anionic Iron Polyphosphides by Reaction of White Phosphorus with “Cp*Fe⁻”

Selective P₄ Activation by a Highly Reduced Cobaltate: Synthesis of Dicobalt Tetraphosphido Complexes

Metalate‐Mediated Functionalization of P₄ by Trapping Anionic [Cp*Fe(CO)₂(η¹‐P₄)]⁻ with Lewis Acids