New Synthetic Strategies for Phosphorus-Containing Cryptands and the First Phosphorus Spherand Type Compound

Phosphorus dendrimers and dendrons functionalized with the cage ligand tris(1,2‐dimethylhydrazino)diphosphane

“…The methylene group located at the middle of the chain appeared as a quintuplet of doublets because of its coupling with the four protons of the methylene groups attached to it ( 3 J HH = 6.9 Hz) and with the P N phosphorus atom ( 4 J HP = 1.5 Hz). A two-dimensional 1 H 13 C HMQC experiment permitted to assign unequivocally the 13 C NMR spectrum of 5 and to correlate each carbon signal of the chain with its corresponding proton atoms. In addition, the 13 C NMR spectra with individual irradiation of the two phosphorus atoms were performed to assign unambiguously the two doublets corresponding to the two different methyl groups of the cage that appeared at 37.8 ( 2 J CP = 10.8 Hz) and 36.2 ppm ( 2 J CP = 2.2 Hz).…”

“…A two-dimensional 1 H 13 C HMQC experiment permitted to assign unequivocally the 13 C NMR spectrum of 5 and to correlate each carbon signal of the chain with its corresponding proton atoms. In addition, the 13 C NMR spectra with individual irradiation of the two phosphorus atoms were performed to assign unambiguously the two doublets corresponding to the two different methyl groups of the cage that appeared at 37.8 ( 2 J CP = 10.8 Hz) and 36.2 ppm ( 2 J CP = 2.2 Hz). Thus, the irradiation of the phosphorus nuclei P N produced the disappearance of the coupling of the carbon signal at 36.2 ppm, indicating that this was the corresponding signal for the closest methyl groups.…”

“…1 H and 13 C NMR spectra were collected to complete the characterization of this compound. As in the case of 5, 13 C NMR spectra with selective irradiation of phosphorus nuclei and two-dimensional 1 H- 13 C HMQC spectrum were essential to complete the assignment of the signals. Unfortunately, neither MALDI nor ES mass spectra confirmed the identity of the compound, due to its high degree of fragmentation, well known for phosphorhydrazonecontaining dendrimers [10].…”

“…The other 31 P shift values remained almost unchanged. In the 13 C NMR spectrum, one methylene carbon appeared coupled with the phosphorus atom (53.5 ppm, d, 2 J CP = 7.9 Hz) SCHEME 4 Synthesis of multifunctional dendrons.…”

Preparation of heteromacrocycles bearing two tetra-coordinate phosphorus atoms and at least two ferrocene units

“…The methodology used is based on the reaction of the bis-azide 3 with diphosphines of general structure R 2 P-Y-PR 2 some of which have been used by Majoral and coworkers for the preparation of phosphorus-containing cryptands. 9 Frequently, the synthesis of macrocycles with chemically diverse donating (or bonding) atoms requires multistep manipulations with concomitantly low yields or difficult separations. However the macrocyclization process following this methodology takes place in a single step, with high yields and without the presence of any template.…”