Silylation of Dinitrogen Coordinated to Transition Metals and its Application to Catalytic Nitrogen Fixation

过渡金属配位二氮的硅烷化及其在催化固氮中的应用

• 批准号: 03453097
• 负责人: HIDAI Masanobu
• 金额: $ 4.42万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1991
• 资助国家: 日本
• 起止时间: 1991 至 1992
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-03453097/
• 关键词: Dinitrogen; Catalysis Silylamine; Silylation; Germylation; Silyldiazenido; Silylhydrazido; タングステン窒素錯体; モリブデン窒素錯体; 配位窒素シリル化反応; シリルアミン

1. Treatment of a dinitrogen complex cis-[W(N_2)_2(PMe_2Ph)_4](1a) with R_3SiCl/NaI mixtures afforded a variety of silyldiazenido complexed trans-[WI(NNSiR_3)(PMe_2Ph)_4], while the reactions of 1a or its Mo analogue 1b with ClSiMe_2CH_2CH_2SiMe_2Cl/NaI resulted in the formation of silylhydrazido(2-) complexes cis, mer-[WI_2(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_3](2). Complex 1a also reacted with R_3GeCl/NaI to give germyldiazenido complexes trans-[WI(NNGeR_3)(PMe_2Ph)_4].2. By treatment with R_3SiCl and Na in the presence of a catalytic amount of 1b, molecular nitrogen has been converted into silylamines under ambient conditions. The yields of silylamines produced by these novel catalytic reactions considerably depended upon the nature of the substituents attached to the Si atom.3. One PMe_2Ph ligand in 2 was replaced readily by a series of pi-acceptor ligands at room temperature, affording various disilylhydrazido(2-) complexes cis, trans-[WI_2(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_2(L)](L = CO, CH_2=CH_2, RCN). In contrast, from the reaction mixture of 2 with 'BuNC a cationic complex mer-[WI(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_3]I has been isolated as the major product. Furthermore, 2 reacted with CH_2X_2 (X = I, Cl) to give paramagnetic W(V) complexes mer, trans-[WX_3(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_2]. Hydrolysis of this W(V) complex (X = I) and the subsequent condensation reaction with ketones afforded new W(V) complexes [WI_3(NNH_2)(PMe_2Ph)_2] and mer, trans-[WI_3(NN=CRR')(PMe_2Ph)_2], respectively.

1.双氮配合物cis-[W（N_2）_2（PMe_2Ph）_4]（1a）与R_3SiCl/NaI混合物反应，得到各种硅基二氮烯配合物trans-[WI（NNSiR_3）（PMe_2Ph）_4]，而1a或其Mo类似物1b与ClSiMe_2CH_2CH_2SiMe_2Cl/NaI反应，则得到硅基肼基（2-）配合物cis，mer-[WI_2（NNSiMe_2CH_2CH_2SiMe_2）（PMe_2Ph）_3]（2）.配合物1a还与R_3GeCl/NaI反应，得到锗基二氮烯配合物trans-[WI（NNGeR_3）（PMe_2Ph）_4]。用R_3SiCl和Na在催化量的1b存在下处理，在室温下，分子氮被转化为硅胺。通过这些新的催化反应生成的硅烷胺的产率在很大程度上取决于连接到Si原子上的取代基的性质。2中的一个PMe_2Ph配体在室温下很容易被一系列π受体配体取代，得到了各种二硅酰肼（2-）配合物cis，transs-[WI_2（NNSiMe_2CH_2CH_2SiMe_2）（PMe_2Ph）_2（L）]（L = CO，CH_2=CH_2，RCN）.相反，从2与'BuNC的反应混合物中分离出阳离子络合物mer-[WI（NNSiMe_2CH_2CH_2SiMe_2）（PMe_2Ph）_3]I作为主要产物。2与CH_2X_2（X = I，Cl）反应生成顺磁性的W（V）配合物mer，trans-[WX_3（NNSiMe_2CH_2CH_2SiMe_2）（PMe_2Ph）_2]。该W（V）配合物（X = I）水解后与酮发生缩合反应，分别得到新的W（V）配合物[WI_3（NNH_2）（PMe_2Ph）_2]和mer，trans-W（V）配合物[WI_3（NN= CRR '）（PMe_2Ph）_2]。

项目成果

Y. Mizobe: "Organic Chemistry of Early Transition Metals" Gakkai Shuppan Center.

Y. Mizobe：“早期过渡金属的有机化学”Gakkai Shuppan 中心。

Andrew C.Street: "Silylation of Coordinated Dinitrogen by Silylcobalt Complexes.Preparation of a New Series of Silyldiazenido and Silylhydrazido(2ー) Complexes of Molybdenum and Tungsten" Chem.Lett.383-386 (1991)

Andrew C.Street：“硅钴配合物对配位二氮的硅烷化。钼和钨的一系列新的硅基二氮烯基和硅基肼基 (2ー) 配合物的制备”Chem.Lett.383-386 (1991)

H.Oshita: "Preparation and Characterization of Paramagnetic W(V) Diazoalkane Complexes mer,trans-[WX_3(NN=CMeR)(PMe_2Ph)_2] (X=Br,I;R=Me,Ph)and Hydrazido(2-) Complex [Wl_3(NNH_2)(PMe_2Ph)_2]." J.Organomet.Chem.

H.Oshita：“顺磁性 W(V) 重氮烷配合物 mer,trans-[WX_3(NN=CMeR)(PMe_2Ph)_2] (X=Br,I;R=Me,Ph) 和 Hydrazido(2-) 的制备和表征

H. Oshita: "Silylation and Germylation of a Coordinated Dinitrogen in cis-[M(N_2)_2(PMe_2Ph)_4] (M = Mo, W) Using R_3ECl/NaI and R_3ECl/Na Mixtures (E = Si, Ge)" J. Organomet. Chem.

H. Oshita：“使用 R_3ECl/NaI 和 R_3ECl/Na 混合物 (E = Si, Ge) 对顺式 [M(N_2)_2(PMe_2Ph)_4] (M = Mo, W) 中的配位二氮进行硅烷化和胚芽化”

H. Oshita: "Novel Disilylation of Dinitrogen Ligand in cis-[W(N_2)_2(PMe_2Ph)_4]. Synthesis and Reactivity of mer-[WI_2(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_3]" Organometallics. 11. 4116-4123 (1992)

H. Oshita：“顺式-[W(N_2)_2(PMe_2Ph)_4]中二氮配体的新型二甲硅烷基化。mer-[WI_2(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_3]的合成和反应性”有机金属化合物。