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

• 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
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10440192/
• 关键词: chalcogen; sulfide; selenide; tungsten; hetero-dimetallic complexes; alkylation; fluxionality; chiral separation; オキソ; アルキル化; 不斉; 光学分割; モリブデン; チオラート; 炭素-硫黄、結合切断; 不斉分割; 反応機構; 炭素-硫黄結合切断; 炭素-硫黄結合生成

( 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）我们从半桥的W-RU和W-RH DINUCLIEL复合物中合成了半sandwich Tungsten Trisuffo Complex（PPH_4）[CP*WS_3]以及各种luthenium and Rhodium Complexs。并已检查异质二元的反应性。例如，我们发现双核氢化物复合物cp*w（m-s）_3ruH（pph_3）_2与1当量的meococCCH反应，从而得到Cp*w（μ-S）_3ru（c（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 equivalent of MeOCOC≡CH in THFgave rise to Cp*W(μ-S_2C_2HCOOMe)(μ-S)Rh(PPh_3)_2, where the alcoholne was added to the terminal S atom and the bridging S atom.( 2 ) We carried out a series of alcohol （PPH_4）末端硫化物的反应[CP*WS_3]。例如，与烯丙基氯化物或元氯化物的反应产生了CP* W（S）_2（Sch_2cr = CH_2）（R = H，ME）。发现它显示了烯丙基硫酸盐群体的引人入胜的磁通行为。为了阐明流量性的机制，我们已新合成（PPH_4）[（ETME_4C_5）W（o）W（o）（s） - （SCH_2CR = CH2）]复合物。 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 occurred 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综合体携带三个不同的Chalcoge原子，（PPH_4）[CP*W（O）（S）（SE）]。此外，我们能够将（pph_4）[cp*w（o）（s）（sr*）]（r*=手性烷基组）分开的非对映异构体，然后与li_2se_2产生的反应给出了enatio-excess（pph_4）[pph_4）[pph_4）[cp*w（o）（s s）（s）（se）（se）。

项目成果

Nagasawa,Takayuki: "Isolation of Pentamethylcyclopentadienyl Tris(ter-butylthiolato) Complexes of Tungsten(IV) and Carbon-Sulfur Bond Activation"J.Organomet.Chem.. 592・1. 46-51 (1999)

长泽隆之：“钨（IV）五甲基环戊二烯基三（叔丁基硫醇）络合物的分离和碳硫键活化”J.Organomet.Chem.. 592・1（1999）。

翼 和行: "無機化学との接点"21世紀の潮流を探る -有機金属分野-. 13-21 (1999)

Kazuyuki Tsubasa：“与无机化学的交叉”探索 21 世纪的趋势 - 有机金属领域 - 13-21 (1999)。

J.-P.Lang, H.Kawaguchi, K.Tatsumi: "Reactions of the Tungsten Tris-sulfido Complex [PPh_4][η^5-C_5Me_5)WS_3] with [M'(PPh_3)_2(NO_3)](M'=Cu(I), Ag(I)), [Au(PPh_3)Cl], and [Pd(dppe)CI_2] : Isolation and Structures of[η^5-C_5Me_3)WS_3Cu_3(PPh_3)_3(NO_3)][NO

J.-P.Lang、H.Kawaguchi、K.Tatsumi：“三硫钨配合物 [PPh_4][η^5-C_5Me_5)WS_3] 与 [M(PPh_3)_2(NO_3)](M =Cu(I)、Ag(I))、[Au(PPh_3)Cl] 和 [Pd(dppe)CI_2]：[η^5-C_5Me_3)WS_3Cu_3(PPh_3)_3(NO_3)] 的分离和结构[不

H. Sugiyama, Y. Hayashi, H. Kawaguchi, K. Tatsumi: "Synthesis of Alkynethiolato and Alkyneselenolato Complexes of Tltanocene (IV) and Samarocene(III)"Inorg. Chem.. 37. 6773-6779 (1998)

H. Sugiyama、Y. Hayashi、H. Kawaguchi、K. Tatsumi：“Tltanocene (IV) 和 Samarocene (III) 的 Alkynethiolato 和 Alkyneselenolato 配合物的合成”Inorg。

S. E. d'Arbeloff, P. B. Hitchcock, J. F. Nixon, T. Nagasawa, H. Kawaguchi, and K.Tatsumi: "[3+2] Cyclo-addition Reactions of the Phospha-alkyne, tBuCP, with Transition Metal Trisulphide Containing Terminal Thio-hgands : Syntheses, Crystal and Molecular St

S. E. dArbeloff、P. B. Hitchcock、J. F. Nixon、T. Nagasawa、H. Kawaguchi 和 K.Tatsumi：“[3 2] 磷酸炔 tBuCP 与含有末端硫配体的过渡金属三硫化物的环加成反应