“…Phosphinine ether macrocycles, the analogues of phosphine-ether macrocycles are designed as flexible and selective ligands in view to obtain host-guest complexes with metal cations [3]. Even if crown ethers and phosphine-ether macrocycles display interesting coordinative behavior towards metals or neutral molecules, due to optical isomerism of phosphorus atoms they posses many practical problems [5][6][7][8][9][10][11][12][13]. The aromatic character of phosphinine was demonstrated earlier by structural and magnetic criteria and also by spectral investigation [14][15][16][17][18].…”
The geometry and electronic structure of several phosphinine-ether macrocycles were investigated at semiempirical level. The calculated geometries are in good agreement with experimental data. Compared to phosphinine, the coordinative abilities of phosphinineether macrocycles based on energy considerations suggest a little lowered π acceptor character, while π donor character is improved. The molecular environment causes a significant mixing of phosphinine and phenyl substituent π levels. The geometry and electronic properties of phosphinine-ether macrocycles can provide significant host coordination properties for guest species.
“…Phosphinine ether macrocycles, the analogues of phosphine-ether macrocycles are designed as flexible and selective ligands in view to obtain host-guest complexes with metal cations [3]. Even if crown ethers and phosphine-ether macrocycles display interesting coordinative behavior towards metals or neutral molecules, due to optical isomerism of phosphorus atoms they posses many practical problems [5][6][7][8][9][10][11][12][13]. The aromatic character of phosphinine was demonstrated earlier by structural and magnetic criteria and also by spectral investigation [14][15][16][17][18].…”
The geometry and electronic structure of several phosphinine-ether macrocycles were investigated at semiempirical level. The calculated geometries are in good agreement with experimental data. Compared to phosphinine, the coordinative abilities of phosphinineether macrocycles based on energy considerations suggest a little lowered π acceptor character, while π donor character is improved. The molecular environment causes a significant mixing of phosphinine and phenyl substituent π levels. The geometry and electronic properties of phosphinine-ether macrocycles can provide significant host coordination properties for guest species.
“…It has been reported that introduction of sulfur donor atoms in these systems could modulate their complexing abilities, and several macrocycles containing a mixed phosphorus−sulfur donor set of atoms could be found in the literature. Most of them incorporate aromatic rings fused in the macrocyclic chain, − but saturated ring systems containing exclusively P x S y donor set of atoms have been less developed. , The present work deals with the synthesis of the first saturated 14-membered diphosphadithia macrocycle 14P 2 S 2 (Scheme ), the separation of its cis and trans isomers, and reactions of these isomers with hydrated Ni(II) perchlorate. 1 …”
The new saturated 14-membered
P2S2 macrocycle
1,8-diphenyl-1,8-diphospha-4,12-dithiacyclotetradecane
(14P2S2) has been synthesized and the
cis- and trans-isomers have been isolated and
characterized. The complexing behavior of these two isomers toward
Ni(II) has been tested, and the crystal structure of the
[Ni(trans-14P2S2)(CH3CN)](ClO4)2
complex has been solved.
“…Von Kyba et al wurde eine ganze Reihe von Dibenzodiphospha-14hcoronanden-4i 6 synthetisiert [9]. Nicht benzoanellierte Phosphacoronanden sind nur wenige bekannt; hierher gehˆren die 18-gliedrigen Makrocyclen 7, die aufgrund der hohen Inversionsbarrieren terti‰rer Phosphine als 5 Diastereoisomere vorliegen, die von Ciampolini getrennt und charakterisiert wurden [10]. Von M‰rkl und Hoferer [11] wurden 1992 erstmals Derivate des 18hO 2 .P-Coronanden-6i 8 (RPh, cyclo-C 6 H 11 ) hergestellt.…”
zum 90. Geburtstag gewidmet Diphosphapodands, [12]-, [15]-, and [18]Diphosphacoronands, Diphosphacryptand-8, and Alkali-Metal ComplexesThe cyclizing bis-phosphonium-salt formation of the open-chain bis-phosphine 17a (1,1,7,7-tetrabenzylhP.O.Ppodand-7i) with diethylene glycol derived dibromide 13a yields the 12-membered cyclic bis-phosphonium salt 20 (4,4,10,10-tetrabenzyl-12hO.P.O.P-coronand-4i-4,10-diium dibromide) in yields as high as 50 ± 60%. The 1,1,10,10-tetrabenzylhP.O 2 .P-podand-10i 17b forms with 13a the 15-membered cyclic bis-phosphonium salt 21 (7,7,13,13-tetrabenzyl-15hO 2 .P.O.P-coronand-5i-7,13-diium dibromide) with the same high yield. By quaternization of the bis-phosphine 17b with triethylene glycol derived dibromide 13b, the 18-membered 7,7,16,16-tetrabenzyl-18hO 2 .P.O 2 .P-coronand-6i-7,16-diium dibromide 24 is obtained in 50% yield, too. The Wittig reaction of the cyclic phosphonium salts with benzaldehyde yields the 12-, 15-, and 18-membered cyclic bisbenzylphosphine dioxides 9, 10, and 11 as cis-and trans-isomers beside trans-stilbene. The 7,13-dioxido-7,13-dibenzyl-15hO 2 .P.O 2 .P-coronand-5i 10 forms a crystalline 1 : 1 Na-complex 23, which exists as a dimer. The structure of 23 was established by an X-ray analysis and spectroscopic data. The 7,16-dibenzyl-18hO 2 .P.O 2 .Pcoronand-6i 28 that is available by reduction of 11 with CeCl 3 /LiAlH 4 reacts with triethylene glycol derived dibromide 13b under RugglyÀZiegler-dilution conditions to give the bicyclic bis-phosphonium salt 29 (1,10-Helvetica Chimica Acta ± Vol. 85 (2002) 1714 1 ) Bei Makrocyclen mit mehreren, insbesondere unterschiedlichen Heteroatomen im Ring f¸hrt die IUPACNomenklatur h‰ufig zu schwer nachvollziehbaren Bezeichnungen. F¸r makrocyclische Polyether hat Pederson [2] deshalb die Kronenether-Nomenklatur als Trivialnomenklatur eingef¸hrt. Bei verschiedenen Ringheteroatomen ebenso wie bei anellierten Ringsystemen ist die Pederson-Nomenklatur ebenfalls nicht mehr eindeutig. Die hier benutzte Coronanden-und Podanden-Nomenklatur wurde von Vˆgtle [5] eingef¸hrt. Hiernach werden offenkettige Systeme mit mehreren Donoratomen, die ebenfalls zur Komplexbildung geeignet sind, als Podanden und monocyclische Systeme mit Donoratomen (z.B. N, S, O) als Coronanden bezeichnet (die Bezeichnung Kronenether ist auf Coronanden beschr‰nkt, die ausschliesslich O-Atome als Donor-Atome besitzen. Sich von den Coronanden ableitende bicyclische Systeme werden als Cryptanden bezeichnet (siehe z.B. 2) [5]. dibenzylhP[O 2 ] 3 .P-cryptand-8i-1,10-diium dibromide) in 18% yield. Again, by the Wittig procedure with benzaldehyde, the 7,16-dioxidohP[O 2 ] 3 P-cryptand-8i 12 is obtained as the first diphosphacryptand. The FD-MS (CH 2 Cl 2 ) of the cyclic bis-phosphine dioxides 10 ± 12 show that they exist as [2M Na] complexes. The complex formation constants K a of 9 ± 11 with alkali-metal cations are studied and compared with the complex formation of corresponding crown ethers.
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