Synthesis of a Complexed 2,2-Bisphosphirane

Vlaar, Mark J. M.; Ehlers, Andreas W.; Kanter, Frans J. J. de; Schakel, Marius; Spek, Anthony L.; Lammertsma, Koop

doi:10.1002/1521-3773(20000818)39:16<2943::aid-anie2943>3.0.co;2-i

Cited by 25 publications

(14 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Only selected dienes and diynes yield the corresponding bisphosphiranes (2) [2] and bisphosphirenes (4). [3] More typical is a P À C insertion of the second complexed phosphinidene into a phosphirene ring, formed by the first [RPM(CO) 5 Multiple [RPM(CO) 5 ] additions from a single source precursor are also known, but these are rare as well.…”

Section: Introductioncontrasting

confidence: 99%

Metal-Template-Directed Synthesis of Diphosphorus Compounds through Intramolecular Phosphinidene Additions

et al. 2002

Self Cite

View full text Add to dashboard Cite

Heating the nonchelating cis-bis-7-phosphanorbornadiene-[Mo(CO)4] complex (13) results in the thermal decomposition of one of the 7-phosphanorbornadiene groups. The phosphinidene thus generated adds intramolecularly to a C=C bond of the other ligand to give the novel diphosphorus complex 14. This reaction constitutes a metal-template-directed synthesis. Likewise, the intramolecular phosphinidene addition to the C=C bond of a Mo-phospholene ligand affords the diphos complex 18. Its crystal structure exhibits an extremely small P-Mo-P bite-angle for a five-membered chelate ring. The similar intramolecular 1,2-addition to a C=C bond of a phosphole ligand gives a highly strained, unstable intermediate product. Scission of its P-Mo bond generates a free coordination site, which is then occupied by either CO or a phosphole to yield complexes 22 and 23, respectively. The analogous intermolecular addition of [PhPW(CO)5] to a [phosphole-W(CO)5] complex gives the di-[W(CO)5] complexed adduct 28. The directing effect of the metal on the intra- and intermolecular additions is discussed.

show abstract

Section: Introductioncontrasting

confidence: 99%

Metal-Template-Directed Synthesis of Diphosphorus Compounds through Intramolecular Phosphinidene Additions

et al. 2002

Self Cite

View full text Add to dashboard Cite

show abstract

“…The next question is whether azaphosphiridines are intermediates in the formation of the bridged diazaphospholanes 10 a ± c. In other words, is a CPN ring indeed formed first, after which the second CN group is inserted intramolecularly, or is there a direct single-step pathway that leads to the diazaphospholanes? We ask this question because only one isomer of the bicyclic products 10 a ± c is formed at 110 8C, which is a temperature at which P-epimerization is known to occur in complexed phosphiranes, [9,10] while isomeric mixtures of 7 a ± c and 12 are obtained for the intermolecular reaction (Scheme 2 and Scheme 4).…”

Section: Resultsmentioning

confidence: 99%

“…It is well recognized that the PÀC bonds of phosphiranes shorten on P-substitution and on complexation by transition metal groups. [9] The geometrical parameters of diazaphospholane 15 resemble those of the crystal structure of 10 b, taking into account that the calculated P À N and P À C bonds are longer, due to the absence of P-substituents and that thermal motion is absent in the calculated structure. However, the deviation in the P-N-C (D 3.18) and N-C-N (D 4.88) angles indicates the presence of steric strain in the highly substituted experimental structure.…”

Section: Resultsmentioning

confidence: 99%

Addition of a Phosphinidene Complex to C=N Bonds: P-Ylides, Azaphosphiridines, and 1,3-Dipolar Cycloadditions

Vlaar¹,

Valkier²,

Kanter³

et al. 2001

Chem. Eur. J.

Self Cite

View full text Add to dashboard Cite

The terminal phosphinidene complex PhPW(CO)5 adds to the imine bond of PhHC=N-Ph to give 3-membered ring azaphosphiridines, which undergo ring-expansion with an additional imine to yield a set of four isomeric five-membered ring diazaphospholanes. Treatment with the diimines PhHC=N-(CH2)n-N=CHPh (n=2,3,4) results instead-in all three cases-in only a single isomer of the (CH2)n bridged diazaphospholane. For n=2 or 3, this aminal group is easily hydrolyzed to afford new 6- and 7-membered ring heterocycles. No intermediate azaphosphiridine complex is observed during the addition reaction to the diimines. B3LYP/6-31G* calculations on an unsubstituted, uncomplexed system suggest that the initially formed P,N-ylide of the H2C=N-(CH)2-N=CH2 diimine both kinetically and thermodynamically favors an intramolecular 1,3-dipolar cycloaddition over an imine insertion into the CPN ring of an intermediate azaphosphiridine. Single-crystal X-ray structures for the (CH2)2-bridged azaphospholane complex and the HCl adduct of the 7-membered hydrolysis product are presented.

show abstract

“…Two alternative reaction courses have also been observed. If the 2-vinylphosphirane displays sufficient thermal stability, it is possible to graft a second phosphinidene unit onto the vinylic double bond to get a 2,2'-biphosphirane [73] In the same vein, allenes and cumulenes react cleanly with terminal-phosphinidene complexes to give 2-alkylidenephosphiranes [76] and phospha [3]radialenes [77], respectively (Eqns. 20 and 21).…”

Section: Generation Of Electrophilicmentioning

confidence: 99%

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

Synthesis of a Complexed 2,2-Bisphosphirane

Abstract: Double addition of the phosphinidene complex [PhPW(CO)5] to 2,5‐dimethyl‐2,4‐hexadiene led to the first bisphosphiranes. The s‐trans conformation of the intermediate vinylphosphiranes prevents rearrangements and epimerizations, but does not hamper a second addition (see scheme).

Cited by 25 publications

References 31 publications

Metal-Template-Directed Synthesis of Diphosphorus Compounds through Intramolecular Phosphinidene Additions

Metal-Template-Directed Synthesis of Diphosphorus Compounds through Intramolecular Phosphinidene Additions

Addition of a Phosphinidene Complex to C=N Bonds: P-Ylides, Azaphosphiridines, and 1,3-Dipolar Cycloadditions

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

Contact Info

Product

Resources

About