Phosphorus–nitrogen compounds. Part 54. The reactions of geminal N3P3(NH2)2Cl4and of N3P3(NH2)Cl5with alkoxide ions in alcohols. The geminal P(NH2)2to non-geminal P(NH2)(OR) rearrangement. The crystal structures of trans-N3P3(NH2)2(OPrn)4, cis-N3P3(NH2)2(OMe)4</

Fincham, J. K.; Parkes, Harold G.; Shaw, L. S.; Shaw, Robert A.; Hursthouse, Michael B.

doi:10.1039/dt9880001169

Cited by 21 publications

(2 citation statements)

References 8 publications

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“…Examples of both types I and II have been examined crystallographically, for example geminal N 3 P 3 Cl 3 (NMe 2 ) 3 , trans -N 3 P 3 Cl 4 (NMe 2 ) 2 , and trans -N 3 P 3 (NH 2 ) 2 (OPr n ) 4 . Additional complications can occur when a chiral molecule, which may be synthesized as a racemate, crystallizes through spontaneous resolution as a chiral crystal.…”

Section: Introductionmentioning

confidence: 99%

Chiral Configurations of Cyclophosphazenes

et al. 2000

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Tetracoordinated phosphorus atoms in derivatives of cyclophosphazenes are pentavalent and are potentially chiral. Chirality does not seem to have been investigated nor discussed for any literature examples of crystal structures of those cyclophosphazene compounds which are expected to be chiral. In cyclotriphosphazatriene compounds with ansa-substituted macrocyclic rings the two phosphorus atoms attached to the macrocycle are chiral, although the cis-ansa cyclotriphosphazatriene-macrocycle 1 is the meso form. Reaction of 1 with the di-secondary amine, piperazine, provides a convenient way to investigate the chiral configurational properties of cyclophosphazene compounds. It is found by X-ray crystallography that there are two configurational isomers (one meso and one racemate) of the singly bridged di(cyclophosphazene-macrocyclic) piperazine derivative 6i, and that there are two configurational isomers (both meso) of the doubly bridged di(cyclophosphazene-macrocyclic) piperazine derivative 8i; in 8i one meso form has a center of symmetry and the other a plane of symmetry. The chiral configurational properties of each stage of the reaction scheme for formation of 6i and 8i from 1 have been confirmed by 31 P NMR spectroscopy and the results are consistent with inversion of configuration at phosphorus at each step of the reaction of >P(OR)Cl groups with HNR′R′′ to form >P(OR)(NR′R′′) derivatives: viz. reaction of 1 with piperazine gives the monosubstituted compound 4i, which exists as a racemate with the macrocyclic ring in the trans-configuration; reaction of compound 4i with 1 gives the two configurational forms (meso and racemate) of the singly bridged derivative 6i with the macrocyclic rings in the trans-trans configuration; reaction of 6i with piperazine gives the monosubstituted singly bridged derivative 7i, which exists as two racemic mixtures with the macrocyclic rings in cis-trans configurations; and intramolecular condensation of 7i gives the two configurational forms of the doubly bridged derivative 8i with each of the macrocyclic rings in the cis-cis configuration. In this work the configurational properties of derivatives of cyclotriphosphazatriene rings with two (one N 3 P 3 unit) or four (two N 3 P 3 units) chiral centers have been rationalized. It is found that the chiral structures of cyclotriphosphazatriene derivatives may be represented by 2D molecular diagrams, as long as the Fischer rules for chiral carbon compounds are followed for phosphorus compounds.

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Section: Introductionmentioning

confidence: 99%

Chiral Configurations of Cyclophosphazenes

et al. 2000

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“…The chlorophosphazene rings, especially (PNCl 2 ) 3 (1) are important precursors of phosphazene polymers. Although a number of cyclic phosphazenes with amino [1][2][3][4][5][6][7], aryloxy [8][9][10][11][12][13], aryl [14] groups have been prepared and studied, discussion on a substitution with pyridine derivatives is relatively limited in the literature [15][16][17][18][19][20]. In this article, we report the reactions of 1 with pyridine derivatives 2-5.…”

Section: Introductionmentioning

confidence: 99%

The reactions of hexachlorocyclotriphosphazatriene with pyridine derivatives

Begeç

Alataş

Kılıç

2006

Heteroatom Chemistry

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Synthesis and Structure of New Carborane‐Substituted Cyclotriphosphazenes

Abizanda

Crespo

Gimeno

et al. 2003

Chemistry A European J

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The reactions of [N(3)P(3)Cl(6)] with one, two, or three equivalents of the difunctional 1,2-closo-carborane C(2)B(10)H(10)[CH(2)OH](2) and K(2)CO(3) in acetone have been investigated. These reactions led to the new spiro-closo-carboranylphosphazenes gem-[N(3)P(3)Cl(6-2n)[(OCH(2))(2)C(2)B(10)H(10)](n)] (n=1 (1), 2 (2)) and the first fully carborane-substituted phosphazene gem-[N(3)P(3)[(OCH(2))(2)C(2)B(10)H(10)](3)] (3). A bridged product, non-gem-[N(3)P(3)Cl(4)[(OCH(2))(2)C(2)B(10)H(10)]] (4), was also detected. The reaction of the well-known spiro derivatives [N(3)P(3)Cl(2)(O(2)C(12)H(8))(2)] and [N(3)P(3)Cl(4)(O(2)C(12)H(8))] with the same carborane-diol and K(2)CO(3) in acetone gave the new compounds gem-[N(3)P(3)(O(2)C(12)H(8))(3-n)[(OCH(2))(2)C(2)B(10)H(10)](n)] (n=1 (5) or 2 (6), respectively), without signs of intra- or intermolecularly bridged species. Upon treatment with NEt(3) in acetone, compound 5 was converted into the corresponding nido-carboranylphosphazene. However, the reaction of gem-[N(3)P(3)(O(2)C(12)H(8))(2)[(OCH(2))(2)C(2)B(10)H(10)]] (5) with NEt(3) in ethanol instead of acetone proceeded in a different manner to give the new compound (NHEt(3))(2)[N(3)P(3)(O(2)C(12)H(8))(2)(O)[OCH(2)C(2)B(9)H(10)CH(2)OCH(2)CH(3)]] (7). For compounds with two 2,2'-dioxybiphenyl units, gem-[N(3)P(3)(O(2)C(12)H(8))(2)[(OCH(2))(2)C(2)B(10)H(10)]] (5), (NHEt(3))[N(3)P(3)(O(2)C(12)H(8))(2)[(OCH(2))(2)C(2)B(9)H(10)]] (8), and (NHEt(3))(2)[N(3)P(3)(O(2)C(12)H(8))(2)(O)[OCH(2)C(2)B(9)H(10)CH(2)OCH(2)CH(3)]] (7), a mixture of different stereoisomers may be expected. However, for 5 and 7 only the meso compounds seem to be formed, with the same (R,S)-configuration as in the precursor [N(3)P(3)Cl(2)(O(2)C(12)H(8))(2)]. The reaction of 5 to give 8 seems to proceed with a change of configuration at one phosphorus center, giving a racemic mixture. The crystal structures of the nido-carboranylphosphazenes 7 and 8 have been confirmed by X-ray diffraction methods.

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Cited by 21 publications

References 8 publications

Chiral Configurations of Cyclophosphazenes

Chiral Configurations of Cyclophosphazenes

The reactions of hexachlorocyclotriphosphazatriene with pyridine derivatives

Synthesis and Structure of New Carborane‐Substituted Cyclotriphosphazenes

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