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    • 1. 发明授权
    • Platinum-nitrogen complex catalysts
    • 铂 - 氮配合物催化剂
    • US4588800A
    • 1986-05-13
    • US689184
    • 1985-01-07
    • Frederick J. PalenskyAllen R. Siedle
    • Frederick J. PalenskyAllen R. Siedle
    • C07F7/14C07F15/00C08G77/38C08L83/04C08G77/06
    • C08G77/38C07F15/0006C07F7/14C08L83/04C08G77/20
    • A hydrosilation process is dislosed for the reaction between silicon-hydrogen bonds and compounds having aliphatic carbon atoms linked by multiple bonds using as catalysts novel platinum-nitrogen complex compounds of the following classes:(a) monometallic complexes, (L)PtX.sub.2 (Y),(b) bimetallic complexes, (L)(PtX.sub.2).sub.2 (Y).sub.2,(c) ionic complexes, (L)PtX.sub.2 (Y)(Z), and(d) reduced forms of said monometallic complexes having the formulae:H[(PNZ)PtX.sub.2 (Q)].sub.2, (1)[(PNZ)PtX.sub.2 (Q)].sub.2.sup.- A.sup.+, (2) and[H(PNZ)PtCl.sub.2 (C.sub.2 H.sub.4)].sub.3 PtCl.sub.3 (3) whereinL is a single or fused ring unsaturated heterocyclic ligand, wherein said hetero atoms are nitrogen, comprising at least one 5- or 6-member ring, said ligand having 2 to 4 nitrogen atoms in the same ring, and said ligand having up to a total of 44 carbon atoms,Y is an uncharged olefinically unsaturated hydrocarbon monodentate ligand that fills only one coordination position of the platinum atom and is selected from olefinically unsaturated hydrocarbons, triarylphosphines or triarylarsines wherein aryl is phenyl or phenyl substituted by up to 4 lower alkyl groups having 1 to 4 carbon atoms, dialkyl sulfides wherein each alkyl group independently has 1 to 16 carbon atoms, and carbon monoxide, the ligand having up to 25 carbon atoms,X is independently Cl, Br, I, CN, or SCN,Z is HCl, HBr, or silver trifluoromethanesulfonate,Q is an aliphatically unsaturated olefin ligand of 2 to 25 carbon atoms,A is a cation, andPNZ is phenazine.Preparation of the novel catalysts is described. The cured compositions are useful in the preparation of molded articles.
    • 硅氢键与具有通过多个键连接的脂族碳原子的化合物之间的反应的氢化硅烷化方法被用作催化剂,以下类别的新型铂 - 氮络合物化合物:(a)单金属络合物,(L)PtX 2(Y) ,(b)双金属络合物,(L)(PtX2)2(Y)2,(c)离子络合物,(L)PtX2(Y)(Z)和(d)所述具有下式的单金属络合物的还原形式: H [(PNZ)PtX2(Q)] 2,(1)[(PNZ)PtX2(Q)] 2-A +,(2)和[H(PN​​Z)PtCl2(C2H4)] 3PtCl3(3) 单环或稠环不饱和杂环配体,其中所述杂原子是氮,其包含至少一个5-或6-元环,所述配体在同一环中具有2-4个氮原子,所述配体具有总共44 碳原子,Y是不饱和的烯属不饱和烃单齿配体,其仅填充铂原子的一个配位位置,并且选自烯属不饱和烃,三芳基膦或 三芳基砜,其中芳基是苯基或被至多4个具有1-4个碳原子的低级烷基取代的苯基,其中每个烷基独立地具有1至16个碳原子的二烷基硫化物,和一氧化碳,具有至多25个碳原子的配体,X 独立地是Cl,Br,I,CN或SCN,Z是HCl,HBr或三氟甲磺酸银,Q是2至25个碳原子的脂族不饱和烯属配体,A是阳离子,PNZ是吩嗪。 描述了新型催化剂的制备。 固化的组合物可用于制备模制品。
    • 2. 发明授权
    • Platinum-nitrogen complex catalysts
    • 铂 - 氮配合物催化剂
    • US4511715A
    • 1985-04-16
    • US402231
    • 1982-07-27
    • Frederick J. PalenskyAllen R. Siedle
    • Frederick J. PalenskyAllen R. Siedle
    • C07F7/14C07F15/00C08G77/38C08L83/04B01J31/22B01J31/24
    • C08G77/38C07F15/0006C07F7/14C08L83/04
    • A hydrosilation process is disclosed for the reaction between silicon-hydrogen bonds and compounds having aliphatic carbon atoms linked by multiple bonds using as catalysts novel platinum-nitrogen complex compounds of the following classes:(a) monometallic complexes, (L)PtX.sub.2 (Y),(b) bimetallic complexes, (L)(PtX.sub.2).sub.2 (Y).sub.2,(c) ionic complexes, (L)PtX.sub.2 (Y)(Z), and(d) reduced forms of said monometallic complexes having the formulae:(1) H[(PNZ)PtX.sub.2 (Q)].sub.2,(2) [(PNZ)PtX.sub.2 (Q)].sub.2.sup.- A.sup.+, and(3) [H(PNZ)PtCl.sub.2 (C.sub.2 H.sub.4)].sub.3 PtCl.sub.3whereinL is a single or fused ring unsaturated heterocyclic ligand, wherein said hetero atoms are nitrogen, comprising at least one 5- or 6-member ring, said ligand having 2 to 4 nitrogen atoms in the same ring, and said ligand having up to a total of 44 carbon atoms,Y is an uncharged olefinically unsaturated hydrocarbon monodentate ligand that fills only one coordination position of the platinum atom and is selected from olefinically unsaturated hydrocarbons, triarylphosphines or triarylarsines wherein aryl is phenyl or phenyl substituted by up to 4 lower alkyl groups having 1 to 4 carbon atoms, dialkyl sulfides wherein each alkyl group independently has 1 to 16 carbon atoms, and carbon monoxide, the ligand having up to 25 carbon atoms,X is independently Cl, Br, I, CN, or SCN,Z is HCl, HBr, or silver trifluoromethanesulfonate,Q is an aliphatically unsaturated olefin ligand of 2 to 25 carbon atoms,A is a cation, andPNZ is phenazine.Preparation of the novel catalysts is described. The cured compositions are useful in the preparation of molded articles.
    • 公开了硅氢键与具有通过多个键连接的脂族碳原子的化合物之间的反应的硅氢化方法,使用以下类别的新型铂 - 氮络合物:(a)单金属络合物,(L)PtX 2(Y) ,(b)双金属络合物,(L)(PtX2)2(Y)2,(c)离子络合物,(L)PtX2(Y)(Z)和(d)所述具有下式的单金属络合物的还原形式: (1)H [(PNZ)PtX2(Q)] 2,(2)[(PNZ)PtX2(Q)] 2-A +和(3)[H(PN​​Z)PtCl2(C2H4)] 3PtCl3,其中L是 单环或稠环不饱和杂环配体,其中所述杂原子是氮,其包含至少一个5-或6-元环,所述配体在同一环中具有2-4个氮原子,所述配体具有总共44 碳原子,Y是不饱和的烯属不饱和烃单齿配体,其仅填充铂原子的一个配位位置,并且选自烯属不饱和烃,三芳基膦或 三芳基砜,其中芳基是苯基或被至多4个具有1-4个碳原子的低级烷基取代的苯基,其中每个烷基独立地具有1至16个碳原子的二烷基硫化物,和一氧化碳,具有至多25个碳原子的配体,X 独立地是Cl,Br,I,CN或SCN,Z是HCl,HBr或三氟甲磺酸银,Q是2至25个碳原子的脂族不饱和烯属配体,A是阳离子,PNZ是吩嗪。 描述了新型催化剂的制备。 固化的组合物可用于制备模制品。
    • 6. 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。