Cationic Group 4 Metallocene–(
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‐Phosphanylaryl)oxido Complexes: Synthetic Routes to Transition‐Metal Frustrated Lewis Pairs
作者:Andy M. Chapman、Mairi F. Haddow、Duncan F. Wass
DOI:10.1002/ejic.201100968
日期:2012.3
Syntheticroutes to cationicgroup 4 metallocene–(o-phosphanylaryl)oxido compounds of the type [CpR2M(OPR2)][WCA] (M = Ti, Zr, Hf; WCA = weakly coordinating anion) are described. The neutral mono-methyl complexes [CpR2ZrMe(OPR2)] 1–6 [CpR = Cp (1–3) or Cp* (4); OPR2 = o-OC6H4(PtBu)2 (1 and 4), OCMe2CH2(PtBu)2 (2) or OC(CF3)2CH2(PtBu)2 (3)] are prepared by protonolysis of [CpR2ZrMe2] by the parent alcohol
Ph; 8, R = tBu). The reactivity of Sc-based Lewispair complexes 6 and 8 toward a wide range of substrates was investigated. A ligand substitution reaction occurred when complex 6 was treated with benzophenone. The reaction of complex 6 with sulfur afforded a phosphane oxidative product. Complexes 6 and 8 also exhibited typical Sc/P frustratedLewispair (FLP) reactivity. They added to the carbonyl
用膦基取代的醇处理a混合的烷基/二芳基氧化物配合物导致形成mixed混合的烷氧基/二芳基氧化物配合物Sc [OC(CH 3)2 CH 2 PR 2 ] [O-2,6- t Bu 2 -C 6 H 3 ] 2 [THF](6,R = Ph;8,R =t Bu)。研究了基于Sc的Lewis对配合物6和8对多种底物的反应性。当配合物6用二苯甲酮处理时,发生配体取代反应。络合物的反应6与硫一起提供膦氧化产物。配合物6和8还表现出典型的Sc / P受阻的路易斯对(FLP)反应性。他们加到异氰酸苯酯的羰基上,形成七元金属环。配合物6与α,β-不饱和羰基化合物进行选择性的Sc / P 1,4-加成反应,得到相应的九元金属环产物。6与0.5 mol乙炔基二羧酸二甲酯的反应导致形成双环[7.7.0] cetane衍生的金属环16,具有独特的双1,4-加成模式。与苯甲配合物6进行1,4-加成反应得到顺式-烯二醇盐,通过Sc-O和P-O键与Sc
Facile dihydrogen release from phosphino-borinate ester Lewis pairs
作者:Andy M. Chapman、Mairi F. Haddow、Jonathan P. H. Orton、Duncan F. Wass
DOI:10.1039/c0dt00513d
日期:——
New phosphino-borinate ester Lewis pairs of the type tBu2PCH2C(R)2OB(C6F5)2 (R = Me or CF3) are synthesised from the corresponding phosphino-alcohol and HB(C6F5)2. Dihydrogen release from the zwitterionic tBu2PHCH2C(R)2OBH(C6F5)2 is facile.
新型膦-硼酸酯Lewis酸碱对tBu2PCH2C(R)2OB(C6F5)2(R = Me 或 CF3)是通过相应的膦-醇与HB(C6F5)2反应合成的。从两性离子的tBu2PHCH2C(R)2OBH(C6F5)2中释放出二氢是容易进行的。