1,4-Addition of a Terminal Phosphinidene Complex to [5]Metacyclophane

Eis, Maurice J. van; Komen, C. M. D.; Kanter, F. J. J. De; Wolf, W. H. De; Lammertsma, Koop; Bickelhaupt, F.; Lutz, Martin; Spek, Anthony L.

doi:10.1002/(sici)1521-3773(19980619)37:11<1547::aid-anie1547>3.0.co;2-s

Cited by 27 publications

(10 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The ratios between the [1 2] and [1 4] cycloaddition products are essentially temperature independent, thus showing that the [1 4] adduct is not formed by rearrangement of the [1 2] adducts. A similar[1 4] cycloaddition has also been observed with a strained benzene derivative whose cyclic delocalization is partly disrupted by the geometrical distortion of the ring[75] (Eqn. 19).…”

supporting

confidence: 52%

Electrophilic Terminal-Phosphinidene Complexes: Versatile Phosphorus Analogues of Singlet Carbenes

Mathey

Huy

Marinetti

2001

HCA

225

View full text Add to dashboard Cite

In memory of Professor Luigi M. Venanzi, a highly respected inorganic chemist Electrophilic and nucleophilic terminal-phosphinidene complexes are compared in terms of electronic structures and reactivities. Various precursors of the unstable electrophilic species [RÀPÀM] (M Cr, Mo, W(CO) 5 and Fe(CO) 4 ) are discussed. The addition reactions of the electrophilic phosphinidene complexes with Lewis bases, insertion reactions into OÀH, NÀH, and activated CÀH bonds, and cycloaddition reactions with double and triple bonds are described, as well as some rearrangements and autocondensations. Various applications to the synthesis of new organophosphorus molecules are discussed and techniques available for demetallation are given.

show abstract

supporting

confidence: 52%

Electrophilic Terminal-Phosphinidene Complexes: Versatile Phosphorus Analogues of Singlet Carbenes

Mathey

Huy

Marinetti

2001

HCA

225

View full text Add to dashboard Cite

show abstract

“…Analysis of the reaction mixture (see the Experimental Section) showed the presence of the four isomers of phosphirane complex 21 (characteristics are summarized in Table ) that must result from addition of [PhPW(CO) 5 ] to one of the double bonds of phosphepine 1a (Scheme ). The addition underscores the olefinic nature of the phosphepine ring of 1a as additions to aromatic rings are rare 9 Reaction of Phosphinidene 5a in the Presence of 1 a at 60 °C 4 21 δ 3 J PP (Hz)W(CO) 5 P2W(CO) 5 P1rel int a −8.4, −126.9 14.7 endo endo 0.46 b −6.6, −118.8 11.7 endo exo 1.00 c −15.5, −123.4 11.4 exo exo 0.59 d −16.4, −127.9 14.6 exo endo <0.1

…”

Section: Resultsmentioning

confidence: 98%

3H-Benzophosphepine Complexes: Versatile Phosphinidene Precursors

et al. 2005

Self Cite

View full text Add to dashboard Cite

The synthesis of a variety of benzophosphepine complexes [R = Ph, t-Bu, Me; ML(n )()= W(CO)(5), Mo(CO)(5), Cr(CO)(5), Mn(CO)(2)Cp] by two successive hydrophosphinations of 1,2-diethynylbenzene is discussed in detail. The first hydrophosphination step proceeds at ambient temperature without additional promoters, and subsequent addition of base allows full conversion to benzophosphepines. Novel benzeno-1,4-diphosphinanes were isolated as side products. The benzophosphepine complexes themselves serve as convenient phosphinidene precursors at elevated, substituent-dependent temperatures (>55 degrees C). Kinetic and computational analyses support the proposal that the phosphepine-phosphanorcaradiene isomerization is the rate-determining step. In the absence of substrate, addition of the transient phosphinidene to another benzophosphepine molecule is observed, and addition to 1,2-diethynylbenzene furnishes a delicate bidentate diphosphirene complex.

show abstract

“…The first and so far only reported addition of a complexed phosphinidene to an aromatic compound is the reaction between PhPW(CO) 5 and [5]metacyclophane ( 58 ) to give the genuine 1,4‐addition product 59 67. Decomplexation of the W(CO) 5 group by I 2 oxidation and N ‐methylimidazole ligand exchange resulted in the unique, moderately stable, free 7λ 3 ‐phosphanorbornadiene 60 68.…”

Section: Reactions Of Electrophilic Phosphinidene Complexesmentioning

confidence: 99%