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    • 5. 发明申请
    • METHOD FOR PRODUCING SILASESQUIOXANE METAL COMPLEXES, NOVEL SILASESQUIOXANE METAL COMPLEXES AND THE USE THEREOF
    • 用于生产silasesquioxane金属络合物新silasesquioxane金属配合物及其用途
    • WO98046352A1
    • 1998-10-22
    • PCT/EP1998/001932
    • 1998-04-02
    • B01J31/02B01J31/12B01J31/16B01J31/22C07D301/02C07D301/03C07F7/08C07F9/00C07F17/00C08G77/398C07D301/00C07F7/28
    • C08G77/398B01J31/125B01J31/1675B01J31/2226B01J2231/70B01J2231/72B01J2531/0205B01J2531/0288B01J2531/46B01J2531/48B01J2531/56C07D301/02C07F7/0836C07F7/0838C07F9/00C07F9/005C07F17/00
    • The invention relates to a method for producing silasesquioxane metal complexes of general formula (II) {R SiO1,5)n(R SiO1,5)m[(B)q(O)r]}u(M)v(Y)w, wherein R stands for C5-C10-cycloalkyl, norbornyl, adamantyl; R means oxygen; B stands for H, OH, halogen, alkoxy, SiR y, wherein R can be C1-C4 alkyl, aryl or substituted silyl groups and y stands for 2 and 3, and R and R can be functionalized; M stands for metals of the IV to VII PSE sub-group; Y stands for C1-C20 alkyl or aryl groups devoid of betahydrogen, silyl, alkoxy, OH, halogen, oxo, imido, fluorenyl, indenyl, cyclopentadienyl, whereby the individual ligands can be substituted; n = 6 and 7; m = 0 and 1; q = 0-2; r = 0-2; u = 1-4; v = 1-4; w = 0-12, wherein a metal compound of the IV to VII PSE sub-group and at least one silasesquioxane of general formula (I) {(R SiO1,5)n(R SiO1,5)m[(H)p(B)q(O)r]}, in which R , B, n, m, q, r have the above-mentioned meaning, and R stands for OH and p equals 0-4, are suspended in an akylated aromatic hydrocarbon, optionally in the presence of a basic compound by stirring at -80 to +110 DEG C and the reaction product is separated at room temperature. The invention also relates to metal complexes which comprise an oxidic metal cluster containing titanium atoms, wherein each titanium atom has been coordinated x 6. The invention also describes the use of said metal complexes as catalysts for the oxidation or epoxidation of unsaturated hydrocarbons or alcohols, also in an aqueous medium.
    • 本发明涉及一种用于制备通式silasesquioxane - 金属配合物(II)的方法:{(R <1>的SiO 1.5)N(R <2A>的SiO 1.5)M [(B)Q(O)R]} U(M)v(Y)W,其中R <1> C5-C10环烷基,降冰片基,金刚烷基,R <2A>氧,BH,OH,卤素,烷氧基,SIR <3>ÿ其中R <3 可以是> C1-C4烷基,芳基或取代甲硅烷基,y为2和3,和R可以被官能化<1>和R <3>中,第四至第七过渡族的PTE的,Y C1-C20的M个金属 不含有的β氢,甲硅烷基,烷氧基,OH,卤素,氧代,亚氨基,芴基,茚基,环戊二烯基,其中每个配体可被取代,n为6和7烷基或芳基,m为0和1,q 0 到2,r为0至2,u为1〜4,v为1至4,w为0至12,由第四至第七子组的金属化合物和通式中的至少一个silasesquioxane反应(I):{R <1> 的SiO 1.5)N(R <2>的SiO 1.5)M [(H)p(B)q(O)R]}其中,R <1>,B,N,M,q,R如上述所定义 具有R <2> OH和p为0至 4悬浮在烷基化芳族烃,可任选在一种碱性化合物的存在下,用在-80搅拌以110℃,将反应产物在室温下分离。 和金属配合物中,其包括含原子的钛氧化金属簇,其中,每个钛原子配位了6倍。 此外,使用这些金属配合物的描述作为催化剂用于不饱和烃类或醇的氧化或环氧化,也在水性介质中。