Syntheses of metal complexes of lower boranes and its development to metal cluster compounds.

低级硼烷金属配合物的合成及其金属簇化合物的开发。

• 批准号: 01470044
• 负责人: SHIMOI Mamoru
• 金额: $ 4.16万
• 依托单位: Tohoku University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-01470044/
• 关键词: Metallaborane; Lower Borane; Coordination Compound; Unidentate; Photochemical Reaction; Metal Carbonyl; Fluxional; 低級ボラン; モノボラン; ボラン錯体; カルボニル錯体; 二座配位

1. B_2H_4・2P(CH_3)_3 has been known to coordinate to a metal through two vicinal hydrogen atoms. However, the central metal ions are only those with d^<10> electron configuration. To elucidate if it can be coordinated to a metal ion with an electron configuration other than d^<10>, we tried to synthesize B_2H_4・2P(CH_3)_3 complexes using photochemical reactions of group 6 transition metal carbonyls. Both [M(CO)_4{B_2H_4・2P(CH_3)_3}] and [M(CO)_5{B_2H_4・2P(CH_3)_3} (M=Cr, Mo, W) were prepared. B_2H_4・2P(CH_3)_3 acts as a bidentate ligand in the former complexes, but as a unidentate in the latter complexes. The latter complexes are not only the first examples in which B_2H_4・2P(CH_3)_3 acts as a unidentate ligand, but also the first ones in which polyborane acts as a unidentate ligand. Dynamic behavior of the complexes in solutions was elucidated using NMR method.2. Although many coordination complexes with anionic monoboranes such as BH_4^-, have been prepared, no complexes in which neu … More tral monoborane is coordinated has been reported yet. Photochemical reaction of group 6 transition metal carbonyls was used for the syntheses of the complexes with neutral monoborane-Lewis base adducts, and complexes, [M(CO)_5(BH_3・L)] (M=Cr, Mo, W ; L=PMe_3. PPh_3, NMe_3) were prepared, and revealed to be unidentate complexes.3. As [Cu{B_2H_4・2P(CH_3)_3}_2]X where Cu (I) was coordinated tetrahedrally by only four hydrogen atoms was synthesized, we investigated to synthesize mixed borane complexes in which Cu (I) is coordinated with only hydrogen atoms. Cu(B_3H_8){B_2H_4・2P(CH_3)_3} was synthesized.4. It was revealed that Wade rule which is effective to predict the structures of cluster compounds is also applicable to the metal complexes obtained in this project. Thus electron-precise borane complexes obtained in our project can also be described as metallaboranes. Unidentate B_2H_4・2P(CH_3)_3 complexes can be regarded model compounds for the parent borane which has not been synthesized yet. Less

1. B_2H_4·2 P（CH_3）_3通过两个相邻的氢原子与金属配位。然而，中心金属离子仅具有d^<10>电子构型。为了阐明B_2H_4·2 P（CH_3）_3是否能与d ~+以外的金属离子配位<10>，我们尝试利用第6族过渡金属羰基化合物的光化学反应合成B_2H_4·2 P（CH_3）_3配合物。合成了[M（CO）_4{B_2H_4·2P（CH_3）_3}]和[M（CO）_5{B_2H_4·2P（CH_3）_3}（M=Cr，Mo，W）。B_2H_4·2 P（CH_3）_3在前一种配合物中是双齿配体，而在后一种配合物中是单齿配体。后者不仅是第一个以B_2H_4·2 P（CH_3）_3为单齿配体的配合物，也是第一个以聚硼烷为单齿配体的配合物。用核磁共振方法研究了配合物在溶液中的动力学行为.虽然已经制备了许多与BH_4^-等阴离子单硼烷的配合物，但没有发现与BH_4^-等阴离子单硼烷的配合物， ...更多信息 本文报道了过渡单硼烷的配位反应。利用第6族过渡金属羰基化合物的光化学反应，合成了它们与中性一硼烷-路易斯碱加合物的配合物[M（CO）_5（BH_3·L）]（M=Cr，Mo，W ; L=PMe_3. PPh_3，NMe_3）的配合物，发现它们是单齿配合物.在合成了Cu（I）只与四个氢原子四面体配位的[Cu{B_2H_4·2 P（CH_3）_3}_2]X的基础上，我们研究了Cu（I）只与氢原子配位的混合硼烷配合物的合成。合成了Cu（B_3H_8）{B_2H_4·2 P（CH_3）_3}.结果表明，Wade规则对预测簇合物的结构是有效的，同样适用于本项目所得到的金属配合物。因此，在我们的项目中获得的电子精确硼烷配合物也可以被描述为金属硼烷。单齿B_2H_4·2 P（CH_3）_3配合物可作为尚未合成的母体硼烷的模型化合物。少

项目成果

Kinji Katoh: "Syntheses,Structures,and Properties of [M(CO)_5(B_2H_4・2PMe_3)] and [M(CO)_4(B_2H_4・2PMe_3)] (M=Cr,Mo,W)." Inorg.Chem.

Kinji Katoh：“[M(CO)_5(B_2H_4・2PMe_3)] 和 [M(CO)_4(B_2H_4・2PMe_3)] (M=Cr,Mo,W) 的合成、结构和性质。” 。

Mamoru Shimoi: "Syntheses,Structures,and Properties of [M(CO)_5(BH_3・L) (M=Cr,Mo,W;L=PMe_3,PPh_3,NMe_3):First Examples of Coordination Compounds of Lewis Base Adducts of Monoborane." Inorg.Chem.

Mamoru Shimoi：“[M(CO)_5(BH_3・L) (M=Cr,Mo,W;L=PMe_3,PPh_3,NMe_3)的合成、结构和性质：路易斯碱加合物的配位化合物的第一个例子”无机化学。”

Mamoru Shimoi: "Syntheses,Structures,and Properties of [M(CO)_5(BH_3・L)](M=Cr,Mo,W;L=PMe_3,PPh_3,NMe_3): First Examples of Coordination Compounds of Lewis Base Adducts of Monoborane." Inorg.Chem.

Mamoru Shimoi：“[M(CO)_5(BH_3・L)](M=Cr,Mo,W;L=PMe_3,PPh_3,NMe_3)的合成、结构和性质：路易斯碱加合物配位化合物的第一个例子Inorg.Chem。

Kinji Katoh: "Syntheses,structures,and Properties of [M(CO)_5(B_2H_4・2PMe_3)] and [M(CO)_4(B_2H_4・2PMe_3)](M=Cr,Mo,W)." Inorg.Chem.

加藤欣二：“[M(CO)_5(B_2H_4・2PMe_3)]和[M(CO)_4(B_2H_4・2PMe_3)](M=Cr,Mo,W)的合成、结构和性质。” 。

Mamoru Shimoi: "Syntheses and Crystal structures of [Cr(CO)_5(B_2H_4・2PMe_3)] and [Cr(CO)_4(B_2H_4・2PMe_3)]:the First Example of a Single Hydrogen Bridge Bond between a Metal and a Polyborane." J.Chem.Soc.,Chem.Commun.,. 1990. 812-813 (1990)

Mamoru Shimoi：“[Cr(CO)_5(B_2H_4・2PMe_3)]和[Cr(CO)_4(B_2H_4・2PMe_3)]的合成和晶体结构：金属和聚硼烷之间单氢桥键的第一个例子” J.Chem.Soc.,Chem.Commun.,. 1990. 812-813 (1990)