Comparison of Phosphorus and Silicon: Hypervalency, Stereochemistry, and Reactivity.

New tricyclic hexacoordinated phosphoranes 1−6 with internal N→P coordination containing ring sizes varying from five to eight membered have been synthesized by oxidative addition of a quinone or a diol to a cyclic phosphite. The bicyclic phosphorane (NC9H6O)P(O2(3,5-t-Bu)2C6H2)((O-2,4-(t-Bu)2C6H2)2CH2)·1/2H2O (7·1/2H2O) has been synthesized by adding the 3,5-di-tert-butyl-o-benzoquinone to the cyclic phosphite. The compound (NC9H6O)P(2,2‘-OC6H4C6H4O)2 (6) results from a novel ring exchange reaction of a phosphorinane by a phosphepin in two ways:  (a) by treating (OCH2CMe2CH2O)P((OC9H6N) with 2,2‘-biphenol/N-chlorodiisopropylamine and (b) by treating (Et2N)P(OCH2CMe2CH2O)(2,2‘-OC6H4C6H4O) with 8-hydroxyquinoline. Treatment of the aminophosphorane (Et2N)P(OCH2CMe2CH2O)(O2C14H8) with 2,4,6-trimethylbenzoic acid led to the unique ester (OCH2CMe2CH2O)P(O){OC14H8O(C(O)-2,4,6-Me3C6H2)} (10). 31P NMR data for the new compounds are discussed with respect to the differing ring sizes and coordination number on phos...

Bi- and Tricyclic Penta- and Hexacoordinated Phosphoranes with Varying Ring Sizes: Synthesis, Structures, and Reactivity

Synthesis of [2]ferrocenophanes containing trivalent diphosphine units

Ligand exchange and reaction mechanisms offluorinated compounds

New Phospholene and Phosphepine Derivatives from λ3-Phosphorus Compounds and Hexafluoroacetone or Perfluorinated α-Diketones



The reaction of the bis(2-chloroethyl)amino-substituted benzoxazaphosphorinone 1 with hexafluoroacetone (HFA) proceeds with insertion of the carbonyl group of HFA into the heterocycle of 1 to form the oxazaphosphepinedione 2. Triethyl phosphite (3) and triphenyl phosphite (4) react with the perfluorinated diketones 5 and 6 with formation of the pentaoxyphosphoranes 7–10 containing a dioxaphospholene ring system. The reaction of the (2-chloroethyl)amino- and bis(2-chloroethyl)amino-substituted 1,3,5,2-triazaphosphorinanediones 11–14 with the perfluorinated diketone C2F5C(:O)C(:O)CF3 (15) furnishes spirophosphorane derivatives with the dioxaphospholene ring system, 16 and 17, in two cases only. Compound 1 and 2-[bis(2-chloroethyl)-amino]-4H-1,3,2-benzodioxaphosphorin-4-one (18) react with the perfluorinated α-diketones 5 and 6 with insertion of the diketones into the heterocycle of 1 and 18 with formation of compounds 19–22 containing dioxa- and oxazaphosphepinone ring systems. The expected oxidative addition of the diketones to λ3P with formation of spirophosphoranes was not observed. Compounds 19–22 were obtained as mixtures of isomers (19a/b–22a/b). Single crystal X-ray structure analyses were conducted on 2 and 9. The seven-membered ring of 2 displays a “tub” conformation, with the O and benzo C atoms lying out of the plane of the other four atoms. The two independent molecules of 9 are similar, but differ in the degree of distortion from trigonal-bipyramidal geometry of phosphorus.

Neue Phospholen- und Phosphepin-Derivate aus λ3-Phosphorverbindungen und Hexafluoraceton oder perfluorierten α-Diketonen

The crystal and molecular structure of the trigonal-bipyramidal pentaoxy-spirophosphorane 1 reveals the smaller influence on the stereochemistry at phosphorus of the six-membered compared with five-membered rings. The large difference between the two axial P[sbnd]O bonds (161.6 and 171.0 pm) and between the three equatorial P[sbnd]O bonds (range 157.7–163.6 pm) is ascribed to the influence of the CF3-groups on the electronegativity of the oxygen atoms.

Molekülstruktur eines stabilen pentaoxy-spirophosphorans mit phospor als brückenkopfatom zwischen einem sechsgliedrigen und einem fünfgliedrigen ring

The tetraoxa(hydro) spirophosphorane, 3 containing a six and five-membered ring is isolated in 66% yield from the reaction of 2-chloro-1,3,2-dioxaphosphorinane, 1 and triethylammonium perfluoropinacolate, 2. Hexaflouroacetone inserts into the P[sbnd]H bond of 3 to form the pentaoxaphosphorane, 6 which is obtained in a different way from phosphite, 5 and hexafluoroacetone. 2-Methoxy-1,3,2-dioxaphosphorinane, 7 and hexafluoroacetone furnish spirophosphorane, 8, the methoxy derivative of 3. 1H and 19F NMR spectra of the phosphoranes show rapid pseudorotation processes equilibrating substituent positions in the trigonal bipyramidal geometry at phosphorus. The 1H NMR data of the six-membered ring are in accord with a time averaged conformation of a flattened chair.

A stable spirocyclic tetraoxa(hydro)-phosphorane containing a six-membered ring

1-Chlorophosphorinane (1) was obtained in a modified literature procedure by P-N-bond cleavage of 1-diethylaminophosphorinane using dichlorophenylphosphine. Compound 1 and sodium yielded the diphosphine 3, which resulted, also from the redox disproportionation of the intermediate 1-fluorophosphorinane. besides 1,1,1-trifluoro-λ5-phosphorinane. Bromine and iodine split the P-P-bond in 3 to furnish 1-bromo (4) and 1-iodophosphorinane (5). respectively. From 1 and LiOCH(CF3)2 or LiOCH2CF3, the phosphinites 6 and 7 were formed. 1-Chlorophosphorinan (1) wurde nach einer modifizierten Literaturmethode durch P[sbnd]N-Bindungsspaltung von 1-Diethylaminophosphorinan mit Dichlorphenylphosphin erhalten. Verbindung 1 und Natrium ergaben das Diphosphin 3, das auch neben 1,1,1-Trifluor-λ5-phosphorinan in einer Redoxdisproportionierungsreaktion aus dem nicht isolierbaren 1-Fluorphosphorinan entstand. Brom und Jod spalten die P[sbnd]P-Bindung in 3 unter Bildung von 1-Brom- (4) bzw. 1-Jod-phosphorinan (5). Aus 1 ...

1-halogenphosphorinane: darstellung und derivate

The reaction of phosphorus trichloride and 1,3-propanediol was reinvestigated. Besides 2-chloro-1,3,2-dioxaphosphorinane 1 3-chloropropyl-dichlorophosphite 2 was formed. Compound 1 and 2 were fluorinated to give the corresponding phosphorinane 3 and the phosphite 4, respectively. Proton NMR spectra were recorded at 360.08 MHz and simulated for 1 and 3. The 4-H and 6-H signals were treated not as first order but as AA' XX' systems.

Henrik Hacklin

Papers

Molekülstruktur eines stabilen pentaoxy-spirophosphorans mit phospor als brückenkopfatom zwischen einem sechsgliedrigen und einem fünfgliedrigen ring

A stable spirocyclic tetraoxa(hydro)-phosphorane containing a six-membered ring

1-halogenphosphorinane: darstellung und derivate

Investigations in the system phosphorus trichloride/1,3-propanediol