Olefin-Cycloaddition des elektrophilen Phosphinidenkomplexes [iPr2N−P=Fe(CO)4]

Wit, Jan B. M.; Eijkel, Gerno T. van; Kanter, F. J. J. De; Schakel, Marius; Ehlers, Andreas W.; Lutz, Martin; Spek, Anthony L.; Lammertsma, Koop

doi:10.1002/(sici)1521-3757(19990903)111:17<2716::aid-ange2716>3.3.co;2-q

Cited by 4 publications

(5 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These low-valent organophosphorus species are isolobal with the well-known carbene and imido complexes − and (stable) cationic [Cp*(CO) n M = PN- i -Pr 2 ] + ( n = 2, M = Ru; n = 3, M = Mo, W), and into stable nucleophilic or Schrock-type reagents . In 1987 Lappert et al reported the first such complexes for group 6 transition metals, i.e., Cp 2 MPR (M = Mo, W; R = Mes* (supermesityl; 2,4,6-tri- tert -butylphenyl), CH(SiMe 3 ) 2 ).…”

Section: Introductionmentioning

confidence: 99%

“…The reactivity of stable, isolated representatives of either Schrock- or Fischer-type phosphinidene complexes has hardly been explored, which is in sharp contrast with the wealth of novel (strained) organophosphorus compounds that could be synthesized from transient electrophilic species. − The most investigated species, zirconocene complex Cp 2 (PMe 3 )ZrPMes*, reacts, for example, like tantalum complex [N 3 N]TaPR (N 3 N = (Me 3 SiNCH 2 CH 2 ) 3 N), in a phospha-Wittig manner with aldehydes and ketones to give phosphaalkenes.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Synthesis of Novel Terminal Iridium Phosphinidene Complexes

et al. 2002

Self Cite

View full text Add to dashboard Cite

Stable, crystalline iridium-complexed phosphinidenes, Cp*(L)IrdPR, are readily synthesized by (a) the reaction of Cp*(L)IrCl 2 (2, L) PPh 3) with LiPHMes* and (b) dehydrohalogenation of Cp*(PH 2 R)IrCl 2 (5, R) Mes*, Is, Mes) with in situ capturing of transient Cp*Irt PR (4) with phosphines, phosphites, arsines, isocyanides, and carbon monoxide (L). Cp*Irt PR eluded direct detection. The X-ray crystal structures are reported for Cp*(PPh 3)IrdPMes* (3) and Cp*(CO)IrdPMes* (15). The more congested 3 has an E configuration for its IrdP bond, whereas 15 is obtained in its Z form. The 31 P NMR chemical shifts and 2 J PP coupling constants are diagnostic for the E and Z forms. More shielded phosphinidene resonances and larger coupling constants are typical for the E isomers. These iridium-complexed phosphinidenes react with gem-diiodides to form phosphaalkenes, but not with carbonyl groups.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis of Novel Terminal Iridium Phosphinidene Complexes

et al. 2002

Self Cite

View full text Add to dashboard Cite

show abstract

“…[7] From cumulenes even stable vinylidenephosphiranes 6 and phospha [3]radialenes 7 were synthesized by this route. [8] Diallenes also give 1,2-adducts, but these convert to dimethylenephospholes 8 [9] via a [1,3]-sigmatropic shift. [10] Alkylidenecyclopropanes with a second heteroatom in the ring are scarcer and the few that are known as intermediates Abstract: Reaction of the transient phosphinidene complexes R-P= W(CO) 5 with N-substituted-diphenylketenimines leads unexpectedly to the novel 2-aminophosphindoles, as confirmed by an X-ray crystal structure determined for one of the derivatives.…”

Section: Introductionmentioning

confidence: 88%

Methylene‐Azaphosphirane as a Reactive Intermediate

Slootweg

Vlaar

Vugts

et al. 2005

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

Reaction of the transient phosphinidene complexes R‐PW(CO)5 with N‐substituted‐diphenylketenimines leads unexpectedly to the novel 2‐aminophosphindoles, as confirmed by an X‐ray crystal structure determined for one of the derivatives. Experimental evidence for a methylene‐azaphosphirane intermediate was found by using the iron‐complexed phosphinidene iPr2N‐PFe(CO)4, which affords the 2‐aminophosphindole together with the novel methylene‐2,3‐dihydro‐1H‐benzo[1,3]azaphosphole. Analysis of the reaction pathways with DFT indicates that the initially formed methylene‐azaphosphirane yields both phosphorus heterocycles by way of a [1,5]‐ or [1,3]‐sigmatropic shift, respectively, followed by a H‐shift. Strain underlies both rearrangements, which causes these remarkably selective conversions that can be tuned by changing the substituents.

show abstract

“…Recently, a new precursor was developed, 3 H -3-benzophosphepine complex 3 (Scheme ), that offers more flexibility in the choice of the transition metal complex. It has also been shown that transient R 2 N−PFe(CO) 4 , generated from Collman's reagent, adds to double bonds, albeit only to terminal ones . Still other precursors have been reported that are capable of transferring (trapping) electrophilic phosphinidene complexes by addition to olefins and alkynes to generate isomeric phosphiranes 5 and phosphirenes 4 (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Decomplexation of Phosphirane and Phosphirene Complexes

et al. 2006

Self Cite

View full text Add to dashboard Cite

Novel transient phosphinidene complex Ph−PMo(CO)4PMe3, generated from a 7-phosphanorbornadiene precursor, adds to CC and C⋮C bonds to give Mo(CO)4PMe3-complexed phosphiranes and phosphirenes. The cis-PMe3 ligand weakens the interaction between the molybdenum complex and the three-membered ring. Under mild CO pressure the Mo(CO)4PMe3 transition metal group detaches from the phosphorus center of the ring structure by selective CO substitution. The resulting byproduct Mo(CO)5PMe3 can be reused in the synthesis of the phosphinidene precursor.

show abstract

Olefin-Cycloaddition des elektrophilen Phosphinidenkomplexes [iPr2N−P=Fe(CO)4]

Cited by 4 publications

References 0 publications

Synthesis of Novel Terminal Iridium Phosphinidene Complexes

Synthesis of Novel Terminal Iridium Phosphinidene Complexes

Methylene‐Azaphosphirane as a Reactive Intermediate

Decomplexation of Phosphirane and Phosphirene Complexes

Contact Info

Product

Resources

About