CREATION AND CATALYTIC PROPERTIES OF ORGANOTRANSITION METAL COMPLEXES BEARING PHOSPHAALKENE LIGANDS

(1) 1,2-二芳基-3,4-二（2,4,6-三-丁基苯基膦烯）环丁烯配体[芳基=4-甲氧基苯基（DPCB-OMe）]的电子和空间性质；苯（DPCB）；用甲基铂（II）和钯（II）配合物研究了4-三氟甲基苯基（DPCB-CF_3）。结果表明，DPCB-Y配体在普通二亚胺和二膦配体之间具有中等量级的给σ能力，但其π-受体能力远强于其他配体。(2)通过对可能的中间体的模型研究和动力学研究，探讨了钯DPCB-OMe配合物催化烯丙醇和苯胺的脱水缩合反应机理（即苯胺的n -烯丙基化）。本文提出了一种以氢钯为中间体的烯丙醇C-O键裂解生成（π-烯丙基）钯配合物的新工艺。(3)含（π-烯丙基）三酸钯的DPCB-OMe配体在温和条件下，能高效催化苯胺中多种烯丙基醚的脱烯化反应，产率高。该配合物还可作为一种高活性催化剂，用于顺式-2-丁烯-1,4-二醇与活性亚甲基化合物的环脱水反应，生成2-乙烯基-2,3-二氢呋喃。(4)制备了[Pd(MeCN)_2(DPCB-Y)](OTf)_2和[Rh(MeCN)_2(DPCB-Y)]（OTf）的阳离子配合物。前者对氨基甲酸苄酯与α，β-不饱和酮的共轭加成反应具有较高的催化活性。(5)含二氯联苯的钯或铜配合物催化芳基卤化物与苯胺、有机锡试剂或氰化锌的交叉偶联。(6)含DPCB-OMe配体的二氯钌配合物与HSiMe_2Ph催化二乙烯基芳烃的高立体选择性硅氢化反应生成（Z，Z）-双（2-硅乙烯基）芳烃。用NBS处理硅氢化产物会引起立体定向的溴去硅化反应，得到几何纯度高的（Z，Z）-双（2-溴乙烯基）芳烃（>98%）。所制得的（Z，Z）-双（2-溴乙基）苯已应用于以2,5-二辛基氧基-1,4-苯二硼酸为原料，采用suzuki - miyura缩聚法合成几何纯度高的全顺式聚苯乙烯（PPVs）。全顺式ppv在溶液和固体中都单向光异构化为相应的反式ppv。这种现象被应用于在石英衬底上直接进行ppv的微尺度图案化。少

(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