A Thermally Stable and Sterically Unprotected Terminal Electrophilic Phosphinidene Complex of Cobalt and Its Conversion to an η-Phosphirene

Sánchez‐Nieves, Javier; Sterenberg, Brian T.; Udachin, Konstantin A.; Carty, Arthur J.

doi:10.1021/ja028303b

Cited by 67 publications

(48 citation statements)

References 28 publications

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“…The PeN bond distance is 1.672(2) A, which is consistent with a nitrogenephosphorus single bond. Bond distances and angles within the three-membered ring are consistent with those of previously characterized phosphirenes [4,13,22,23]. Compound 2 reacts with styrene to form the phosphirane complex [CpFe(CO) 2 {P(N-i-Pr 2 )CH(Ph)CH 2 }][AlCl 4 ] (4a, b) (Scheme 2).…”

Section: Cycloaddition Reactionssupporting

confidence: 81%

“…Since then a wide range of stable electrophilic terminal phosphinidene complexes have been synthesized [13e16]. The reactivity of stable, cationic phosphinidene complexes has not been as well studied as that of the neutral transient species, but examples of nucleophilic addition [17], bond activation [18], and cycloaddition reactions [13,16] have been described.…”

Section: Introductionmentioning

confidence: 99%

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Formation of phosphorus heterocycles using a cationic electrophilic phosphinidene complex

Vaheesar

Kuntz

Sterenberg

2013

Journal of Organometallic Chemistry

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Section: Cycloaddition Reactionssupporting

confidence: 81%

Section: Introductionmentioning

confidence: 99%

Formation of phosphorus heterocycles using a cationic electrophilic phosphinidene complex

Vaheesar

Kuntz

Sterenberg

2013

Journal of Organometallic Chemistry

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“…Rearrangement reactions of functionalized phosphinidene complexes. A different route to electrophilic "Fischer Type" phosphinidene complexes of molybdenum, tungsten, ruthenium and cobalt was devised by Carty et al [11,41,42] Their approach was based on the chloride abstraction from preformed chloro(diisopropylamino)phosphanido complexes 70a,b, 72, and 74 by using the Lewis acid aluminum chloride (Scheme 30). So far, the reactivity studies of these cations are limited to alkyne additions.…”

Section: Electrophilic Phosphinidene Complexesmentioning

confidence: 99%

Phospha‐ and Arsaalkenes RE=C(NMe₂)₂ (E = P, As) as Novel Phosphinidene‐ and Arsinidene‐Transfer Reagents

Weber

2007

Eur J Inorg Chem

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Phosphinidenes (phosphanylidenes) (RP) are electronically and coordinatively unsaturated phosphorus compounds, which, as six-electron species, are formally analogous to the more familiar carbenes and nitrenes. In contrast to carbenes (CR 2 ), the extremely reactive phosphinidenes cannot be isolated without decomposition. Thus, our knowledge on phosphinidenes is mainly limited to trapping reactions and quantum-chemical calculations. There are a number of synthetic methods for phosphinidenes available, for example photolysis or thermolysis of cyclic phosphanes and oligophosphanes,

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“…Exceptions to these rules include several electron deficient 62 e "square" M 4 frameworks such as [Ru 4 (CO) 10 (µ-CO)(µ 4 -PR) 2 ] (2) and a class of "electronrich" butterfly 64 e molecules (3) such as [Ru 4 (CO) 13 (µ-PR 2 ) 2 ], which exhibit one or more elongated metal-metal bonds. On the other hand, in the PSEPT framework, the 7 skeletal electron pair (SEP) count of [Ru 4 (CO) 10 (µ-CO)(µ 4 -PPh) 2 ] is consistent with the square M 4 (or closo M 4 P 2 ) polyhedron, whereas the 8 SEP molecules [Co 4 (CO) 10 (µ 4 -PR) 2 ] with a similar square Co 4 structure are electron rich (4). There are other anomalies within the 60-64 e regime including a 64-electron (8 SEP) puckered square framework in [Ru 4 (CO) 12 (µ 4 -PNR 2 ) 2 ] where the nonconical nature of the ligands contributes to metal framework distortions (2c, 5).…”

Section: Introductionmentioning

confidence: 98%

Synthesis and transformations of 60-, 62-, and 64-electron Co₄(CO)_x(PNR₂)₂(x= 8, 9, 10) clusters

Sánchez‐Nieves¹,

Sterenberg²,

Udachin³

et al. 2004

Can. J. Chem.

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A unique family of bis-(amino)phosphinidene Co 4 clusters with electron counts in the 60-64 e regime is described. The 62-electron (5 Co-Co) butterfly compound [Co 4 (CO) 8 (µ-CO){µ 3 -P(TMP)} 2 ] (TMP = 2,2,6,6-tetramethylpiperidyl) (1a) is obtained via condensation of the bridged (amino)phosphinidene complex [Co 2 (CO) 6 {µ-P(TMP)}]. Further heating and removal of CO gives the 60-electron (6 Co-Co) tetrahedral compound [Co 4 (CO) 6 (µ-CO) 2 {µ 3 -P(TMP)} 2 ] (3a). The reaction of K[Co(CO) 4 ] with PCl 2 (N-i-Pr 2 ) gives the 64-electron (4 Co-Co) square-planar derivative [Co 4 (CO) 8 (µ-CO) 2 (µ 4 -PN-i-Pr 2 ) 2 ] (2), which loses one carbonyl ligand to form the 62-electron (5 Co-Co) butterfly compound [Co 4 (CO) 8 (µ-CO)(µ 3 -PN-i-Pr 2 ) 2 ] (1b). Complex 1b releases another carbonyl to form the 60-electron (6 Co-Co) tetrahedral compound [Co 4 (CO) 6 (µ-CO) 2 (µ 3 -PN-i-Pr 2 ) 2 ] (3b). X-ray structural analyses of compounds 1a, 1b, 2, and 3a have been carried out. The reversibility of the CO elimination reactions and the structural rearrangements accompanying changes in electron count in this series are discussed. Résumé :On décrit une famille unique d'agrégats de la famille du bis-(amino)phosphinidène Co 4 comportant de 60 à 64 électrons. Le composé en forme de papille comportant 62 électrons (5 Co-Co), le [Co 4 (CO) 8 (µ-CO){µ 3 -P(TMP)} 2 ] (TMP = 2,2,6,6-tétraméthylpipéridyl) (1a) est obtenu par condensation du complexe (amino)phosphinidène ponté [Co 2 (CO) 6 {µ-P(TMP)}]. Un chauffage additionnel avec élimination du CO conduit au composé tétraédrique à 60 élec-trons (6 Co-Co) [Co 4 (CO) 6 (µ-CO) 2 {µ 3 -P(TMP)} 2 ] (3a). La réaction du K[Co(CO) 4 ] avec le PCl 2 (N-i-Pr 2 ) 2 conduit au dérivé plan carré à 64 électrons (4 Co-Co) [Co 4 (CO) 8 (µ-CO) 2 (µ 4 -PN-i-Pr 2 ) 2 ] (2) qui perd un ligand carbonyle pour former le composé en forme de papillon comportant 62 électrons (5 Co-Co), le [Co 4 (CO) 8 (µ-CO)(µ 3 -PN-i-Pr 2 ) 2 ] (1b). Le composé 1b perd un autre ligand carbonyle pour former le composé tétraédrique à 60 électrons (6 Co-Co) [Co 4 (CO) 6 (µ-CO) 2 (µ 3 -PN-i-Pr 2 ) 2 ] (3b). On a déterminé les structures des composés 1a, 1b, 2 et 3a par diffraction des rayons X. On discute de la réversibilité des réactions d'élimination du CO et des réarrangements de structure qui accompagnent les changements dans les nombres d'électrons dans ces séries.

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A Thermally Stable and Sterically Unprotected Terminal Electrophilic Phosphinidene Complex of Cobalt and Its Conversion to an η-Phosphirene

Cited by 67 publications

References 28 publications

Formation of phosphorus heterocycles using a cationic electrophilic phosphinidene complex

Formation of phosphorus heterocycles using a cationic electrophilic phosphinidene complex

Phospha‐ and Arsaalkenes RE=C(NMe₂)₂ (E = P, As) as Novel Phosphinidene‐ and Arsinidene‐Transfer Reagents

Synthesis and transformations of 60-, 62-, and 64-electron Co₄(CO)_x(PNR₂)₂(x= 8, 9, 10) clusters

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A Thermally Stable and Sterically Unprotected Terminal Electrophilic Phosphinidene Complex of Cobalt and Its Conversion to an η-Phosphirene

Cited by 67 publications

References 28 publications

Formation of phosphorus heterocycles using a cationic electrophilic phosphinidene complex

Formation of phosphorus heterocycles using a cationic electrophilic phosphinidene complex

Phospha‐ and Arsaalkenes RE=C(NMe2)2 (E = P, As) as Novel Phosphinidene‐ and Arsinidene‐Transfer Reagents

Synthesis and transformations of 60-, 62-, and 64-electron Co4(CO)x(PNR2)2(x= 8, 9, 10) clusters

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Phospha‐ and Arsaalkenes RE=C(NMe₂)₂ (E = P, As) as Novel Phosphinidene‐ and Arsinidene‐Transfer Reagents

Synthesis and transformations of 60-, 62-, and 64-electron Co₄(CO)_x(PNR₂)₂(x= 8, 9, 10) clusters