Synthesis and Reactivity of an End‐Deck <i>cyclo</i>‐P<sub>4</sub> Iron Complex

Cavaillé, Anthony; Saffon‐Merceron, Nathalie; Nebra, Noel; Fustier‐Boutignon, Marie; Mézailles, Nicolas

doi:10.1002/ange.201711130

Cited by 19 publications

(2 citation statements)

References 48 publications

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“…Contrastingly, mononuclear, or so‐called end‐deck, cyclo ‐P 4 complexes (Scheme ), in which the bonding interactions between the metal center and the cyclo ‐P 4 unit are potentially more simplified, remain uncommon. There are currently only eight structurally characterized end‐deck cyclo ‐P 4 complexes, all of which are either neutral or monoanionic in charge, and are limited to the metals V, Nb, Ta, Mo, Fe, and Co . However, the charge of these mononuclear complexes can create an inherent ambiguity (rather than simplification) of the bonding interactions between the metal and the cyclo ‐P 4 unit.…”

Section: Methodsmentioning

confidence: 99%

Dianionic Mononuclear Cyclo‐P₄ Complexes of Zero‐Valent Molybdenum: Coordination of the Cyclo‐P₄ Dianion in the Absence of Intramolecular Charge Transfer

et al. 2019

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Relative to other cyclic poly‐phosphorus species (that is, cyclo‐Pn), the planar cyclo‐P4 group is unique in its requirement of two additional electrons to achieve aromaticity. These electrons are supplied from one or more metal centers. However, the degree of charge transfer is dependent on the nature of the metal fragment. Unique examples of dianionic mononuclear η4‐P4 complexes are presented that can be viewed as the simple coordination of the [cyclo‐P4]2− dianion to a neutral metal fragment. Treatment of the neutral, molybdenum cyclo‐P4 complexes Mo(η4‐P4)I2(CO)(CNArDipp2)2 and Mo(η4‐P4)(CO)2(CNArDipp2)2 with KC8 produces the dianionic, three‐legged piano stool complexes, [Mo(η4‐P4)(CO)(CNArDipp2)2]2− and [Mo(η4‐P4)(CO)2(CNArDipp2)]2−, respectively. Structural, spectroscopic, and computational studies reveal a similarity to the classic η6‐benzene complex (η6‐C6H6)Mo(CO)3 regarding the metal‐center valence state and electronic population of the planar‐cyclic ligand π system.

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Section: Methodsmentioning

confidence: 99%

Dianionic Mononuclear Cyclo‐P₄ Complexes of Zero‐Valent Molybdenum: Coordination of the Cyclo‐P₄ Dianion in the Absence of Intramolecular Charge Transfer

et al. 2019

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“…[1,2] In the past decades, numerous complexes with various phosphorusa nd polyphosphorus ligandsd erived from P 4 have been isolated and characterized. [3][4][5][6] However,i nm ost cases, the experimental results are unpredictablea nd confusing. [7] Hence, to understand the versatile reaction patterns of P 4 at the molecular level, theoretical studies on P 4 activation are clearly necessary,h elpful, andm eaningful.…”

Section: Introductionmentioning

confidence: 99%

Fragmentation Mechanism of White Phosphorus: A Theoretical Insight into Multiple Cleavage/Formation of P−P and P−C Bonds

Luo

Wang

et al. 2020

Chemistry A European J

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Molecular-level understanding of metal-mediated white phosphorus (P 4)a ctivation is meaningful but challenging because of its direct relevance to the conversion of P 4 into useful organophosphorus compounds as well as the complicateda nd unforeseeable cleavage process of PÀP bonds. The related study,h owever,h as still rarely been achieved to date. Here, at heoretical insighti nto the stepby-step process of three PÀPb ond cleavage/four PÀCb ond formation for [P 3 + +P 1 ]-fragmentation of P 4 mediated by lutetacyclopentadienes is reported. The unique charge-separated intermediate and the intermolecular cooperation between two lutetacyclopentadienes play av ital role in the subsequentP ÀP/PÀCb ondb reaking/forming. It is found that, although the first PÀCf ormation is involved in the assembly of the cyclo-P 3 [R 4 C 4 P 3 ] À unit, the construction of the aromatic five-membered P 1 heterocycle [R 4 C 4 P] À is completed prior to the cyclo-P 3 formation. The reaction mechanism has been carefully elucidated by analyses of the geometric structure, frontier molecular orbitals, bond index,and natural charge, which greatly broaden and enrich the general knowledge of the direct functionalization of P 4 .

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Photolytic Reductive Elimination of White Phosphorus from a Mononuclear cyclo‐P₄ Transition Metal Complex

et al. 2018

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Synthesis and Reactivity of an End‐Deck cyclo‐P₄ Iron Complex

Cited by 19 publications

References 48 publications

Dianionic Mononuclear Cyclo‐P₄ Complexes of Zero‐Valent Molybdenum: Coordination of the Cyclo‐P₄ Dianion in the Absence of Intramolecular Charge Transfer

Dianionic Mononuclear Cyclo‐P₄ Complexes of Zero‐Valent Molybdenum: Coordination of the Cyclo‐P₄ Dianion in the Absence of Intramolecular Charge Transfer

Fragmentation Mechanism of White Phosphorus: A Theoretical Insight into Multiple Cleavage/Formation of P−P and P−C Bonds

Photolytic Reductive Elimination of White Phosphorus from a Mononuclear cyclo‐P₄ Transition Metal Complex

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Synthesis and Reactivity of an End‐Deck cyclo‐P4 Iron Complex

Cited by 19 publications

References 48 publications

Dianionic Mononuclear Cyclo‐P4 Complexes of Zero‐Valent Molybdenum: Coordination of the Cyclo‐P4 Dianion in the Absence of Intramolecular Charge Transfer

Dianionic Mononuclear Cyclo‐P4 Complexes of Zero‐Valent Molybdenum: Coordination of the Cyclo‐P4 Dianion in the Absence of Intramolecular Charge Transfer

Fragmentation Mechanism of White Phosphorus: A Theoretical Insight into Multiple Cleavage/Formation of P−P and P−C Bonds

Photolytic Reductive Elimination of White Phosphorus from a Mononuclear cyclo‐P4 Transition Metal Complex

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Synthesis and Reactivity of an End‐Deck cyclo‐P₄ Iron Complex

Dianionic Mononuclear Cyclo‐P₄ Complexes of Zero‐Valent Molybdenum: Coordination of the Cyclo‐P₄ Dianion in the Absence of Intramolecular Charge Transfer

Dianionic Mononuclear Cyclo‐P₄ Complexes of Zero‐Valent Molybdenum: Coordination of the Cyclo‐P₄ Dianion in the Absence of Intramolecular Charge Transfer

Photolytic Reductive Elimination of White Phosphorus from a Mononuclear cyclo‐P₄ Transition Metal Complex