Decomplexation of Phosphirane and Phosphirene Complexes

Assema, S.G.A. van; Kanter, F. J. J. De; Schakel, Marius; Lammertsma, Koop

doi:10.1021/om060570t

Cited by 24 publications

(15 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In order to analyze the electronic effects of the ligands on allylic alkylation and Suzuki coupling reactions, complexes 1a-Mo(CO) 5 , 1b-Mo(CO) 5 , 1d-Mo(CO) 5 , 2a-Mo(CO) 5 , 2b-Mo(CO) 5 , 2d-Mo(CO) 5 and the known Ph 3 P-Mo(CO) 5 were prepared according to the procedure reported by Lammertsma and co-workers by oxidative removal of a CO from Mo(CO) 6 followed by in situ complexation with the phosphine ligands [7]. These complexes were also fully characterized with 1 H, 13 C and 31 P NMR and HRMS; their IR spectra were recorded and A 1 2 IR frequencies of them were identified.…”

Section: Resultsmentioning

confidence: 99%

“…Following the procedure for the preparation of 2a, compound 2b was synthesized in 60% yield as a deep red sticky solid: R f = 0.24 (hexanes); 1 H NMR (C 6 D 6 ) 7.67 (d, 1H, J = 10 Hz, Ph), 7.16 (d,1H,J = 8.8 Hz,Ph),7.01 (dd,1H,J = 8.4,3.6 Hz,Ph) This complex was prepared following reported procedure [7]. Mo(CO) 6 (316.6 mg, 1.18 mmol) and Me 3 N=O (131.6 mg, 1.18 mmol) in an oven-dried 2-necked round-bottomed flask were dried under vacuum, and the flask was back-filled with nitrogen.…”

Section: -(Diethylphosphino)indenyl-pentamethylcyclopentadienyliron mentioning

confidence: 99%

See 1 more Smart Citation

Steric and Electronic Effects of Benzoferrocenyl Phosphine Ligands on Palladium-Catalyzed Allylic Alkylation and Suzuki Coupling Reactions

Thimmaiah¹,

Luck²,

Fang³

2008

TOOCJ

View full text Add to dashboard Cite

Abstract:Five benzoferrocenyl phosphine ligands with the phosphorus atom attached to the 5-position of the benzoferrocene and some ligand-Mo(CO) 5 complexes were prepared and fully characterized; the structure of one ligand was confirmed by X-ray crystallography. These ligands were applied in palladium-catalyzed allylic alkylation and Suzuki coupling of chlorobenzene with phenylboronic acid. Results were compared with those reported previously using ligands having the phosphorus atom attached to the 4-position of benzoferrocene. This structural modification resulted in an increase of activity of the ligands in allylic alkylation reaction but a decrease of activity in Suzuki coupling reactions. The underlying reasons are analyzed with the help of X-ray single crystal determined structures and CO stretching frequencies in the IR spectra of complexes between the ligands and Mo(CO) 5 .

show abstract

Section: Resultsmentioning

confidence: 99%

Section: -(Diethylphosphino)indenyl-pentamethylcyclopentadienyliron mentioning

confidence: 99%

Steric and Electronic Effects of Benzoferrocenyl Phosphine Ligands on Palladium-Catalyzed Allylic Alkylation and Suzuki Coupling Reactions

Thimmaiah¹,

Luck²,

Fang³

2008

TOOCJ

View full text Add to dashboard Cite

show abstract

“…The importance and uses of phosphirenes are also evident as Ajulu et al 14 use phosphirene as reactants to form complex ring structures. Van Assema and coworkers 15 discuss the in situ creation of phosphinidene active species that react with alkenes and alkynes to yield phosphiranes and phosphirenes, respectively; in this case, the catalyst is molybdenum. The unique properties of phosphiranes also provide impetus for study, as when compared with common phosphines they have increased resistance to oxidation, and also act as better π‐acceptors 16.…”

Section: Introductionmentioning

confidence: 99%

Copper‐catalyzed phosphinidene transfer to ethylene, acetylene, and carbon monoxide: A computational study

Amme

Kazi

Cundari

2009

Int J of Quantum Chemistry

View full text Add to dashboard Cite

ABSTRACT:A DFT study of phosphinidene transfer by copper model catalysts is reported. PR-transfer pathways are highly exergonic with respect to catalyst and phosphinidene transfer reagent. Calculated free energy barriers by which (dhpe)Cu(PMe) active species yields functionalized products are reasonable for modeled substrates-ethylene, acetylene, and carbon monoxide. Calculations suggest a (dhpe)Cu I (-PMe⅐ Ϫ ) formulation as more appropriate than (dhpe)Cu II (ϭPMe 2Ϫ ). The preferred pathway for production of phosphirane (phosphirene) is via direct [1 ϩ 2] addition of ethylene (acetylene) to the PMe group of (dhpe)Cu(PMe), which contrasts the [2 ϩ 2] mechanism for the reaction of ethylene with Ni 0 -phosphinidenes. In light of simulations for neutral and cationic models, it is concluded that the extra electron in copper destabilizes [2 ϩ 2] pathways. Calculated energetics for (dhpe)Cu(PMe) versus (en)Cu(PMe), dhpe ϭ 1,2-bis(dihydrophosphino)ethane, en ϭ ethylenediamine, indicate that the former is a more potent for PR-transfer. Thus, it is inferred that modifications that result in a more electron deficient metal center will yield better group transfer catalysts.

show abstract

“…[150][151][152][153][154][155][156][157] Several decomplexation techniques have also been developed to obtain the free phosphiranes from the coordinated ones. [158][159][160]…”

Section: Scheme 159 Reaction Of Dipotassium Cyclooctatetraenide Withmentioning

confidence: 99%

New aspects of phosphirane chemistry

Feny¹

View full text Add to dashboard Cite

This thesis provides a detailed account of author's exploration on new aspects of phosphirane chemistry. Chapter one briefly reviews the theoretical and experimental works on phosphiranes that have been published until the middle of 2014. Chapter two describes the investigation on the influence of additional strain on phosphiranes. The subjects of the investigation are norbornane-annulated 1-methylphosphirane complexes. The stereochemistry of these complexes has further strained the annulated phosphiranes, leading to a number of structural distortions and selective decomplexation by CO under pressure. Chapter two also recounts the serendipitous discovery of phosphorus dimers from the thermolysis of 7-allyl-7phosphanorbornadiene complex. Chapter three illustrates the study on the activation of 1chlorophosphirane by aluminium trichloride. The subject of the study is cyclohexane-annulated 1-chlorophosphirane complex. It undergoes AlCl 3-catalysed electrophilic aromatic substitution with thiophene and ferrocene to produce 1-(2-thienyl)-and 1-ferrocenylphosphirane complexes respectively. In the absence of electron-rich arenes, a P-C bond cleavage catalysed by AlCl 3 takes place yielding dichloro(cyclohexyl)phosphine complex. The transient ferrocenylphosphinidene complex can be generated from 1-ferrocenylphosphirane complex and trapped with diphenylacetylene, trans-stilbene and water. 1.4.4 Formation of Two P-C Bonds 1.5 Conclusion References Chapter 2. Highly Strained Annulated Phosphiranes 2.1 Introduction 2.2 Results and Discussion 2.3 Conclusion 2.4 Experimental References Chapter 3. Activation of 1-Chlorophosphirane Complex by Aluminium Trichloride 3.1 Introduction 3.2 Results and Discussion 3.3 Conclusion 3.4 Experimental References Appendix vi LIST OF SCHEMES Scheme 1.1 Ring opening of aziridine-2-t-butyl carboxylate by primary amine Scheme 1.2 Copper-catalyzed ring expansion of vinyl oxirane Scheme 1.3 Ring cleavage by HCl or MeOH at room temperature Scheme 1.4 Hydrolysis of phosphirane with lone-pair-bearing substituent on ring carbon Scheme 1.5 Reaction of phospha[3]radialenes with dichlorophosphines Scheme 1.6 Ring-opening of phosphirane oxide by lithium amide Scheme 1.7 Ring opening of phosphirane tungsten complex by lithium amide Scheme 1.8 Synthesis of 1-phosphapentadienyl complex from 2-vinylphosphirane complex Scheme 1.9 Ring-opening of phosphirane complex via nucleophilic attack at phosphorus Scheme 1.10 Mechanism of ring opening of phosphiranes Scheme 1.11 Reaction of vinylphosphirane with methylenetrimethylphosphorane Scheme 1.12 Phosphirane-vinylphosphine rearrangement Scheme 1.13 Rearrangement of 2-chlorophosphirane into vinylchlorophosphine Scheme 1.14 Synthesis of triafulvene with phosphaspiropentene as intermediate Scheme 1.15 Ring opening of phosphiranium salt Scheme 1.16 Cationic ring-opening polymerisation of phosphirane vii Scheme 1.17 Thermal cleavage of phosphirane oxide Scheme 1.18 Thermal splitting of phosphirane yielding chloro(methylene)phosphine Scheme 1.19 Photolysis of 1-mesitylphos...

show abstract

Decomplexation of Phosphirane and Phosphirene Complexes

Cited by 24 publications

References 38 publications

Steric and Electronic Effects of Benzoferrocenyl Phosphine Ligands on Palladium-Catalyzed Allylic Alkylation and Suzuki Coupling Reactions

Steric and Electronic Effects of Benzoferrocenyl Phosphine Ligands on Palladium-Catalyzed Allylic Alkylation and Suzuki Coupling Reactions

Copper‐catalyzed phosphinidene transfer to ethylene, acetylene, and carbon monoxide: A computational study

New aspects of phosphirane chemistry

Contact Info

Product

Resources

About