Cyclotetraphosphinophosphonium ions: Synthesis, structures, and pseudorotation

被引:23
作者
Dyker, C. Adam
Riegel, Susanne D.
Burford, Neil [1 ]
Lumsden, Michael D.
Decken, Andreas
机构
[1] Dalhousie Univ, Atlantic Reg Magnet Resonance Ctr, Dept Chem, Halifax, NS B3H 4J3, Canada
[2] Univ New Brunswick, Dept Chem, Fredericton, NB E3A 6E2, Canada
关键词
D O I
10.1021/ja070764f
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The first derivatives of catenated cyclotetraphosphinophosphonium cations, [(PhP)(4)PPhMe](+) (8a), [(MeP)(4)PMe2](+) (8b), [(CyP)(4)PPh2](+) (8d), [(CyP)(4)PMe2](+) (8e), [(PhP)(4)PPh2](+) (8f), [(PhP)(4)PMe2](+) (8g), are synthesized as trifluoromethanesulfonate (triflate, OSO2CF3-) salts through the reaction of cyclopentaphosphines (PhP)(5) (4a) or (MeP)(5) (4b) with methyl triflate (MeOTf) or by a net phosphenium ion [PR2+, R) Ph, Me; from R2PCI and trimethylsilyltriflate (Me3SiOTf)] insertion into the P-P bond of either cyclotetraphosphine (CyP)(4) (3c) or cyclopentaphosphines (PhP)(5) (4a) or (MeP)(5) (4b). Although more conveniently prepared from 4a, compound 8a[OTf] can also be formed from (PhP)(4) (3a) and MeOTf, and derivatives 8f[OTf] and 8g[OTf] are also accessible through reactions of 3a and R2PCI/Me3SiOTf with R) Ph or Me, respectively. A tetrachlorogallate salt of [(PhP)(4)(PPhBu)-Bu-t](+) (8c) has been synthesized by alkylation of 4a with (BuCI)-Bu-t/GaCI3. P-31{H-1} NMR parameters for all derivatives of 8 have been determined by iterative simulation of experimental data. Derivatives 8a[OTf], 8b[OTf], 8c[GaCl4], 8e[OTf], 8f[OTf], and 8g[OTf] and have been characterized by X-ray crystallography, showing the most favorable all-trans configuration of substituents for the phosphine centers, thus minimizing steric interactions. Each derivative adopts a unique envelope or twist conformation of C-1 symmetry. The effective C-2 symmetry observed for 8b, d, e, f, and g in solution, signified by their P-31{H-1} NMR AA ' BB ' X spin systems, implies a rapid conformational exchange for derivatives of 8. The core frameworks of the cations in the solid state are viewed as snapshots of different conformational isomers within the solution-phase pseudorotation process.
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页码:7464 / 7474
页数:11
相关论文
共 54 条
[1]  
ALBRAND JP, 1978, CR ACAD SCI C CHIM, V287, P89
[2]  
ALBRAND JP, 1974, CHEM COMMUN, P644
[3]   CONFORMATIONAL-ANALYSIS OF SUGAR RING IN NUCLEOSIDES AND NUCLEOTIDES - NEW DESCRIPTION USING CONCEPT OF PSEUDOROTATION [J].
ALTONA, C ;
SUNDARALINGAM, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1972, 94 (23) :8205-+
[4]  
[Anonymous], 1999, SAINT 602
[5]   REACTION OF CYCLOPHOSPHANES WITH CARBON-TETRACHLORIDE AND AMINES [J].
APPEL, R ;
MILKER, R .
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 1975, 417 (03) :161-170
[6]   A synthetic and structural study of the formation of cyclic [(RP)nE]- anions and Zintl compounds using E(NMe2)3 (E = As, Sb) [J].
Bashall, A ;
Beswick, MA ;
Choi, N ;
Hopkins, AD ;
Kidd, SJ ;
Lawson, YG ;
Mosquera, MEG ;
McPartlin, M ;
Raithby, PR ;
Wheatley, AAEH ;
Wood, JA ;
Wright, DS .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2000, (04) :479-486
[7]   Reactions of metallated cyclohexyl phosphine (CyPHM) with As(NMe2)3;: synthesis of [(CyP)4As]- anions (M = Li or Na, Cy = cyclohexyl) [J].
Bashall, A ;
García, F ;
Hopkins, AA ;
Wood, JA ;
McPartlin, M ;
Woods, AD ;
Wright, DS .
DALTON TRANSACTIONS, 2003, (06) :1143-1147
[8]   CONTRIBUTIONS TO THE CHEMISTRY OF PHOSPHORUS .201. PENTAETHYLCYCLOPENTAPHOSPHANE MONOSULFIDE, (PET)5S - PREPARATION AND STRUCTURE DETERMINATION BY P-31 NMR-SPECTROSCOPY [J].
BAUDLER, M ;
KOCH, P .
ZEITSCHRIFT FUR NATURFORSCHUNG SECTION B-A JOURNAL OF CHEMICAL SCIENCES, 1989, 44 (10) :1167-1170
[9]   CONTRIBUTIONS TO THE CHEMISTRY OF PHOSPHORUS .118. CHAIN AND RING PHOSPHORUS-COMPOUNDS - ANALOGIES BETWEEN PHOSPHORUS AND CARBON-CHEMISTRY [J].
BAUDLER, M .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1982, 21 (07) :492-512
[10]   CHEMISTRY OF PHOSPHORUS .218. MONOCYCLIC AND POLYCYCLIC PHOSPHANES [J].
BAUDLER, M ;
GLINKA, K .
CHEMICAL REVIEWS, 1993, 93 (04) :1623-1667