Effect of π-accepting substituent on the reactivity and spectroscopic characteristics of triarylbismuthanes and triarylbismuth dihalides
作者:A.F.M. Mustafizur Rahman、Toshihiro Murafuji、Motoko Ishibashi、Youhei Miyoshi、Yoshikazu Sugihara
DOI:10.1016/j.jorganchem.2004.07.055
日期:2004.10
Competitive chlorination of p-substituted triarylbismuthanes 1 [(p-XC6H4)3Bi; a: X = OMe, c: Cl, d: CO2Et, e: CF3, f: CN, g: NO2] and trimesitylbismuthane (2,4,6-Me3C6H2)3Bi 1h by sulfuryl chloride was carried out against 1b (X = H) and the effect of these substituents on the formation of triarylbismuth dichlorides 2 was studied. The relative ratios 2/2b decreased with increasing electron-withdrawing
对取代的三芳基双muthanes 1 [(p -XC 6 H 4)3 Bi;的竞争氯化。a:X = OMe,c:Cl,d:CO 2 Et,e:CF 3,f:CN,g:NO 2 ]和三甲基异丁烷(2,4,6-Me 3 C 6 H 2)3 Bi 1h通过对1b进行了磺酰氯(X = H),并且研究了这些取代基对二氯化三芳基铋2形成的影响。相对比率2 / 2b的与增加的取代基的吸电子能力(减小2A / 2B = 53/47,图2c / 2b的 = 33/67,2D / 2B = 35/65,2E / 2B = 29/71,2F / 2B = 16/84,2克/ 2B = 0/100,2H / 2b的 = 46/54),表明孤对在铋原子上的反应性降低。钯催化的2a - g及其二氟化物3的降解生成联芳基4受到赤道芳基基团中吸电子p取代基的促进,但被顶端位置上更多带负电的氟原子所抑制。这与三角