CREATION AND CATALYTIC PROPERTIES OF ORGANOTRANSITION METAL COMPLEXES BEARING PHOSPHAALKENE LIGANDS

含磷烯配体有机过渡金属配合物的制备及其催化性能

基本信息

批准号：
15350060
负责人：
OZAWA Fumiyuki
金额：
$ 9.15万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2005
项目状态：
已结题

项目摘要

(1)Electronic and steric properties of 1,2-diaryl-3,4-bis(2,4,6-tri-t-butylphenylphosphinidene)cyclobutene ligands [aryl=4-methoxyphenyl (DPCB-OMe) ; phenyl (DPCB) ; 4-trifluoromethylphenyl (DPCB-CF_3)] have been investigated using their methylplatinum(II) and palladium(II) complexes. It has been found that DPCB-Y ligands possess intermediate magnitude of σ-donating ability between common diimine and diphosphine ligands, but be much stronger π-acceptors than the other supporting ligands.(2)The mechanism of dehydrative condensation of allylic alcohols and aniline (i.e. N-allylation of aniline) catalyzed by palladium DPCB-OMe complex has been examined by model studies of possible intermediates as well as kinetic investigations. A novel process involving a hydridopalladium intermediate has been proposed for C-O bond cleavage of allylic alcohol to give (π-allyl)palladium complexes.(3)(π-Allyl)palladium triflate bearing DPCB-OMe ligand efficiently catalyzes deallylation of a variety of ally … More l ethers in aniline to give corresponding alcohols in high yields under mild conditions. The same complex serves as a highly active catalyst for cyclodehydration of cis-2-butene-1,4-diol with active methylene compounds to give 2-vinyl-2,3-dihydrofurans.(4)Cationic complexes of the formula [Pd(MeCN)_2(DPCB-Y)](OTf)_2 and [Rh(MeCN)_2(DPCB-Y)](OTf) have been prepared. The former shows high catalytic activity towards conjugate addition of benzyl carbamate to α,β-unsaturated ketones.(5)Palladium or copper complexes bearing DPCB catalyze cross-coupling of aryl halides with anilines, organotin reagents, or zinc cyanide.(6)Dichlororuthenium complex bearing DPCB-OMe ligand catalyzes highly stereoselective hydrosilylation of diethynylarenes with HSiMe_2Ph to give (Z,Z)-bis(2-silylethenyl)arenes. Treatment of the hydrosilylation products with NBS causes bromodesilylation in a stereospecific manner, giving (Z,Z)-bis(2-bromoethenyl)arenes with high geometrical purities (>98%). (Z,Z)-Bis(2-bromoethenyl)benzenes thus obtained have been applied to the synthesis of geometrically pure all-cis poly(phenylene vinylene)s (PPVs), which are synthesized by Suzuki-Miyaura-type polycondensation with 2,5-dioctyloxy-1,4-benzenediboronic acid. The all-cis PPVs undergo one-way photoisomerization to the corresponding trans-PPVs both in solution and in the solid. This phenomenon is applied to direct microscale patterning of PPVs onto a quartz substrate. Less

（1）1,2-二芳基-3,4-双（2,4,6-tri-t-tri-t-丁基苯基磷酸二苯基）环丁烯配体[芳基= 4-甲氧基苯基（DPCB-ome）的电子和空间特性；苯基（DPCB）;已经使用其甲基铂（II）和钯（II）配合物研究了4-三氟甲基苯基（DPCB-CF_3）。已经发现，dpcb-y配体具有常见的二亚胺和双氨胺配体之间的中等程度的降低能力，但与其他支撑配体相比，π型的强度要强得多。（2）通过脱水的降温机制，通过降低了dresline andicalline and iniline。通过可能中间体以及动力学研究的模型研究对复合物进行了研究。 A novel process involving a hydridopalladium intermediate has been proposed for C-O bond cleavage of allic alcohol to give (π-allyl)palladium complexes.(3)(π-Allyl)palladium triflate bearing DPCB-OMe ligand efficiently catalyzes deallylation of a variety of … More l ethers in aniline to give corresponding alcohols in high yields under mild conditions.相同的复合物用作高度活性的催化剂，用于用活性亚甲基化合物的Cis-2-丁烯-1,4-二醇循环水，可得到2-乙烯基-2,3-二氢呋喃。（4）配方奶粉的阳离子复合物[pd（mecn）_2（mecn）_2（dpcb-y）（dpcb-y）（dpcb-y）（dpcb-y）（dpcb-y）（dpcb-y）（dpcb-y）（dpcb-y）（otf）_2和2和[RH（MECN）_2（DPCB-Y）]（OTF）已准备好。前者表现出高催化活性，以促进碳酸苯甲酸苯甲酸苯甲酸苯甲酸苯甲酸酯向α，β-未饱和酮。（5）含有DPCB的钯或铜络合物催化芳基卤化物与苯胺，有机蛋白，有机蛋白，有机蛋白或含量cyanide的含量（6）Cateyem cateymectim cateyem catere capenty。用hsime_2ph的二乙基尼拉烯氢化化给出（z，z）-bis（2-二甲二甲苯基）领域。用NBS处理氢硅烷化产物会以立体特异性的方式引起溴化作用，从而给出（Z，Z）-BIS（2-溴乙烯基）领域，具有高几何纯度（> 98％）。（Z，Z）-BIS（2-溴乙烯基）苯苯已应用于几何纯纯的全盘聚（苯基乙烯基乙烯基）S（PPV）的合成，由suzuki-miyaura-type type type type typemontation与2,5-二 - 二氧化型 - 5,5-二氧化型1,4-benzy-benzy-benzy-benzy-benzy-4-benzenzens合成。全CIS PPV在溶液和固体中都经历了对相应的反式PPV的单向光异构化。该现象用于将PPV的直接微观图案化为石英底物。较少的