Reactive E=C(p-p)-pi systems .43. Synthesis and characterization of P-phosphino or P-arsino substituted fluorophosphaalkenes of the type R(2)E-P=C(F)NEt(2) (R=Me, CF3,Me(2)N; E=P, As)

被引:0
作者
Grobe, J
LeVan, D
Winnemoller, J
Krebs, B
Lage, M
机构
来源
ZEITSCHRIFT FUR NATURFORSCHUNG SECTION B-A JOURNAL OF CHEMICAL SCIENCES | 1996年 / 51卷 / 06期
关键词
phosphaalkenes; 1,2,3-triphosphetenes; NMR spectra; crystal structure;
D O I
暂无
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The easily accessible phosphaalkene HP=C(F)NEt(2) (1b) reacts with halophosphanes or -arsanes R(2)EX (X = Cl, I) in the presence of NEt(3) to give P-phosphino- or -P-arsino substituted fluorophosphaalkenes of the type R(2)E-P=C(F)NEt(2) (2-6) in high yields (60-85%) [R(2)E: (CF3)(2)P (2), Me(2)N(CF3)P (3), Me(2)P (4), (CF3)(2)As (5), Me(2)As (6)]. The analogous reaction of 1b with CF3PI2 (molar ratio 1:2) unexpectedly leads to the triphosphetene Et(2)N-C=P-PCF3-PCF3 (7). The stability of compounds 2-6 as a function of R(2)E decreases from As to P and from CF3 to Me, respectively. Compounds 2-6 generally show the Z-configuration and have been characterized by thorough spectroscopic investigations (MS, IR; H-1, F-19, C-13, P-31 NMR). A single crystal X-ray diffraction study of 2 proves the pi-type interaction of the nitrogen lone pair with the P=C bond thus enhancing the stability of the system and the PP bond order.
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页码:778 / 784
页数:7
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