Ring Expansion of a Cp* Moiety: Formation of a 1,2‐Diphosphacyclooctatetraene Ligand

Scheer, Manfred; Himmel, Daniel; Johnson, Brian; Kuntz, Christian; Schiffer, Michael

doi:10.1002/anie.200605173

Cited by 34 publications

(27 citation statements)

References 80 publications

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“…The pnictinidene complexes [Cp*E{W(CO) 5 } 2 ] (E=P, As) are known to show a versatile reaction behavior. Thus, by Cp* migration, an intermediate with a W≡P triple bond is formed, and the elimination of the Cp* substituents results in highly reactive radical species [⋅E{W(CO) 5 } 2 ] . However, the pnictinidene complexes are also electrophilic and can react with nucleophiles to yield new heterocycles .…”

Section: Methodsmentioning

confidence: 94%

“…Nonetheless, also stable phosphinidene complexes can deliver one P atom, however, in a multicomponent ring insertion reaction. Thus, the reaction of the phosphaalkyne MesC≡P with the phosphinidene complex [Cp*P{W(CO) 5 } 2 ] ( 1 a ) led to an insertion of the PC unit of the phosphaalkyne, and of the P atom of the phosphinidene, into the Cp* ring of the phosphinidene complex to form a 1,2‐diphosphacyclooctatetraene ligand …”

Section: Methodsmentioning

confidence: 99%

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Ring Expansions of Nonpolar Polyphosphorus Rings

Piesch

Seidl

Stubenhofer

et al. 2019

Chemistry A European J

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The reaction of the phosphinidene complex [Cp*P{W(CO)5}2] (1 a) (Cp*=C5Me5) with the anionic cyclo‐Pn ligand complex [(η3‐P3)Nb(ODipp)3]− (2, Dipp=2,6‐diisopropylphenyl) resulted in the formation of [{W(CO)5}2{μ3,η3:1:1‐P4Cp*}Nb(ODipp)3]− (3), which represents an unprecedented example of a ring expansion of a polyphosphorus‐ligand complex initiated by a phosphinidene complex. Furthermore, the reaction of the pnictinidene complexes [Cp*E{W(CO)5}2] (E=P: 1 a, As: 1 b) with the neutral complex [Cp′′′Co(η4‐P4)] (Cp′′′=1,2,4‐tBu3C5H2) led to a cyclo‐P4E ring (E=P, As) through the insertion of the pentel atom into the cyclo‐P4 ligand. Starting from 1 a, the two isomers [Cp′′′Co(μ3,η4:1:1‐P5Cp*){W(CO)5}2] (5 a,b), and from 1 b, the three isomers [Cp′′′Co(μ3,η4:1:1‐AsP4Cp*){W(CO)5}2] (6 a–c) with unprecedented cyclo‐P4E ligands (E=P, As) were isolated. The complexes 6 a–c represent unique examples of ring expansions which lead to new mixed five‐membered cyclo‐P4As ligands. The possible reaction pathways for the formation of 5 a,b and 6 a–c were investigated by a combination of temperature‐dependent 31P{1H} NMR studies and DFT calculations.

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Section: Methodsmentioning

confidence: 94%

Section: Methodsmentioning

confidence: 99%

Ring Expansions of Nonpolar Polyphosphorus Rings

Piesch

Seidl

Stubenhofer

et al. 2019

Chemistry A European J

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“…The ditungsten complex 5 reacts with phosphaalkynes (RC≡P) under thermal activation (Scheme 76) [106]. 5 ] which is generated upon heating at 383 K (see Section 5.2.6).…”

Section: Reactions With Molecules Containing Ce Multiple Bonds (E = mentioning

confidence: 99%

Phosphinidene-bridged binuclear complexes

Garcı́a

García‐Vivó

Ramos

et al. 2017

Coordination Chemistry Reviews

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This article contains a comprehensive review of the work carried out within the last three decades on the synthesis, structural studies and reactivity of the binuclear complexes of transition and lanthanide elements bearing bridging phosphinidene (PR) ligands. The latter are grouped into three different classes according to their geometry and electronic distribution: pyramidal, symmetric planar trigonal and asymmetric planar trigonal. Different reactivity patterns can be then outlined for each of these classes of metal complexes, which differ in many ways from those characterizing the extensively studied chemical behaviour of mononuclear phosphinidene complexes.

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“…11 Only if MesC P reacts with 1a, a ring expansion of the Cp* substituent has been found so far. 12 In a recent study, 13 we observed that by using primary phosphines an addition to the Lewis acidic pentelidene atom occurs. So, a type A complex is formed that undergoes an intramolecular hydrophosphination reaction that leads to B.…”

mentioning

confidence: 94%

“…Hydrogen atoms of the methyl groups are omitted for clarity. Selected bond lengths [Å ] and angles [1]: W(1)-P(1) 2.5217(9), W(2)-P(2) 2.5491(10), As(1)-P(1) 2.3463(10), As1(2)-P(2) 2.3770(10), P(1)-C(11) 1.897(4), As1(2)-C(13) 2.060(4), P(2)-C (21) 1.903(3), C(14)-C (15) 1.345(5), P(1)-As1(1)-P(2) 102.14(3), C(11)-P(1)-As(1) 94.80 (12), C(13)-As(1)-P(1) 85.93(10), C(13)-As1(1)-P(2) 101.18(10). ways are possible for the phosphorus derivative.…”

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confidence: 99%

Stepwise activation of “non-innocent” Cp* substituents – a Cp* based cascade reaction

et al. 2012

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Reactions of Cp* substituted pentelidene complexes with the primary phosphine Cp*PH 2 yield novel polycyclic phosphorus/ arsenic and carbon containing cage compounds via cascade-like reactions. These reactions include a sequence of nucleophilic addition reactions, intramolecular hydrophosphination (partially hydroarsination) reactions, retro-Diels-Alder reactions with Cp*H elimination and subsequent [2+4]-cycloadditions.

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Ring Expansion of a Cp* Moiety: Formation of a 1,2‐Diphosphacyclooctatetraene Ligand

Cited by 34 publications

References 80 publications

Ring Expansions of Nonpolar Polyphosphorus Rings

Ring Expansions of Nonpolar Polyphosphorus Rings

Phosphinidene-bridged binuclear complexes

Stepwise activation of “non-innocent” Cp* substituents – a Cp* based cascade reaction

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