Activation and Reactions of Chalcogen Ligands at Early Transition Metal Centers

早期过渡金属中心硫属配体的活化和反应

基本信息

批准号：
10440192
负责人：
TATSUMI Kazuyuki
金额：
$ 8.51万
依托单位：
Nagoya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 2000
项目状态：
已结题

项目摘要

( 1 ) We have synthesized a series of S-bridged W-Ru and W-Rh dinuclear complexes from the reactions of the half-sandwich tungsten trisuffido complex (PPh_4)[Cp*WS_3] and various ruthenium and rhodium complexes. And reactivity of the hetero-dimetallic has been examined. For instance, we have found that the dinuclear hydride complex Cp*W(m-S)_3RuH(PPh_3)_2 reacts with 1 equiv of MeOCOC≡CH to give Cp*W(μ-S)_3Ru(C(=CH_2)COOMe)(PPh_3)_2. On the other hand, the reaction between Cp*W(S)(μ-S)_2-Rh(PPh_3)_2 and 1 equiv of MeOCOC≡CH in THFgave rise to Cp*W(μ-S_2C_2HCOOMe)(μ-S)Rh(PPh_3)_2, where the alkyne was added to the terminal S atom and the bridging S atom.( 2 ) We carried out a series of alkylation reactions at a terminal sulfide of (PPh_4)[Cp*WS_3]. For instance, the reaction with allychloride or methallychloride produced Cp* W(S)_2(SCH_2CR=CH_2) (R = H, Me). which was found to show intresting fluxional behavior of the allylthiolate group. In order to elucidate the mechanism of the fluxionality, we have newly synthesized (PPh_4)[(EtMe_4C_5)W(O)(S)-(SCH_2CR=CH2)] and (PPh_4)[(Me_5C_5)W(O)(S) (SeCH_2CR=CH_2)], and have analyzed variable-temperature ^1H NMR spectra of these complexes. The allyl group of (PPh_4)[(EtMe_4C_5)W(O)(S)- (SCH_2CR=CH_2)] was found to migrate between the two S sites, while the 1,3-allyl shift occured at Se in the case of (PPh_4) (Me_5C_5)W(O)(S)(SeCH_2CR=CH_2)].( 3 ) We have successfully synthesized the halfsandwich tungsten complex which carries three different chalcoge atoms, (PPh_4)[Cp*W(O)(S)(Se)]. Furthermore, we were able to separate the diastereomers of (PPh_4)[Cp*W(O)(S)(SR*)] (R* = chiral alkyl group), and the subsequent reaction with Li_2Se_2 gave enatio-excess (PPh_4)[Cp*W(O)(S)(Se)].

(1)我们通过半夹心钨三硫配合物(PPh_4)[Cp*WS_3]与各种钌、铑配合物的反应合成了一系列S桥联的W-Ru和W-Rh双核配合物。例如，我们已经研究了异质二金属配合物。 Cp*W(m-S)_3RuH(PPh_3)_2 与 1 当量的 MeOCOC≡CH 反应，得到 Cp*W(μ-S)_3Ru(C(=CH_2)COOMe)(PPh_3)_2。 Cp*W(S)(μ-S)_2-Rh(PPh_3)_2 和 1 当量的 MeOCOC≡CH 之间THF产生Cp*W(μ-S_2C_2HCOOMe)(μ-S)Rh(PPh_3)_2，其中炔烃被添加到末端S原子和桥接S原子上。(2)我们在(PPh_4)[Cp*WS_3]的末端硫化物例如与烯丙基氯或甲代烯丙基氯反应生成Cp*。 W(S)_2(SCH_2CR=CH_2) (R = H, Me) 发现烯丙基硫醇基团具有有趣的流动行为，为了阐明流动性的机制，我们新合成了 (PPh_4)[(。 EtMe_4C_5)W(O)(S)-(SCH_2CR=CH2)] 和(PPh_4)[(Me_5C_5)W(O)(S)(SeCH_2CR=CH_2)]，并分析了这些配合物的变温^1H NMR谱。(PPh_4)[(EtMe_4C_5)W(O)的烯丙基。发现 (S)- (SCH_2CR=CH_2)] 在两个 S 位点之间迁移，而 1,3-烯丙基转移在(PPh_4) (Me_5C_5)W(O)(S)(SeCH_2CR=CH_2)]的情况下，发生在Se处。( 3 ) 我们成功合成了携带三种不同碳原子的半夹心钨配合物，(PPh_4)[Cp *W(O)(S)(Se)] 此外，我们能够分离非对映异构体。 (PPh_4)[Cp*W(O)(S)(SR*)] (R* = 手性烷基)，随后与 Li_2Se_2 反应得到对映体过量 (PPh_4)[Cp*W(O)(S) （Se）]。