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    • 19. 发明授权
    • Fluorochemical rhodium compounds
    • 含氟化合物铑化合物
    • US4556720A
    • 1985-12-03
    • US541129
    • 1983-10-12
    • Allen R. SiedleRichard D. Howells
    • Allen R. SiedleRichard D. Howells
    • B01J31/00C07B31/00C07B35/08C07B37/10C07B41/06C07B61/00C07C1/00C07C2/48C07C5/22C07C5/25C07C11/00C07C15/00C07C45/00C07C45/50C07C67/00C07F15/00
    • C07F15/008C07C17/281C07C2/48C07C45/50C07C5/2293C07C5/2593C07C2531/22C07C2531/24
    • Coordination compounds of rhodium are solid salts having donor ligands of [(aryl).sub.3 P].sub.3 Rh.sup.+ and a non-coordinated counterion derived from a fluorochemical acid, the salts having the formula:[(aryl).sub.3 P].sub.3 Rh.sup.+ (counterion).sup.-.The salts are prepared by reacting [(aryl).sub.3 P].sub.4 RhH, which is an uncharged rhodium hydride, with a fluorochemical acid selected form acids having the formulae:HC(R)(SO.sub.2 R.sub.f).sub.2, R.sub.f 'SO.sub.3 H, and HN(SO.sub.2 R.sub.f).sub.2wherein R.sub.f and R.sub.f ' are perfluoroalkyl groups and R is lower alkyl substituted or unsubstituted phenyl, hydrogen, Cl, SO.sub.2 R.sub.f or R.sub.f. Carbonylation of the [(aryl).sub.3 P].sub.3 Rh.sup.+ (counterion).sup.- compounds of this invention, e.g., by contacting the salts of the invention with carbon monoxide gas, produces salts having the formula:[(aryl).sub.3 P].sub.3 Rh(CO).sub.n.sup.+ (counterion).sup.-,wherein n is 1 or 2, and (counterion).sup.- is as defined above. These carbonylated derivatives as well as the above-described precursor salts are useful as catalysts in organic transformation reactions, such as isomerization, cyclization and hydroformylation reactions.
    • 铑的配位化合物是具有[(芳基)3P] 3Rh +的供体配体和衍生自含氟化合物酸的非配位抗衡离子的固体盐,其具有下式:[(芳基)3 P] 3Rh +(抗衡离子) - 。 通过使不饱和氢化铑的[(芳基)3 P] 4RhH与选自具有下列通式的酸的含氟化合物反应来制备盐:HC(R)(SO 2 R f)2,Rf'SO 3 H和HN(SO 2 R f) 2其中Rf和Rf'是全氟烷基,R是低级烷基取代或未取代的苯基,氢,Cl,SO2Rf或Rf。 [(芳基)3P] 3Rh +(抗衡离子)化合物的羰基化,例如通过使本发明的盐与一氧化碳气体接触,产生具有下式的盐:[(芳基)3 P] 3Rh(CO)n + (抗衡离子) - ,其中n为1或2,和(抗衡离子) - 如上所定义。 这些羰基化衍生物以及上述前体盐可用作有机转化反应中的催化剂,例如异构化,环化和加氢甲酰化反应。