Reactivity of the unsaturated dihydrides [Mn2(.mu.-H)2(CO)6(.mu.-L2)] (L2 = Ph2PCH2PPh2, (EtO)2POP(OEt)2) toward boron hydrides. X-ray crystal structure of [Mn2(.mu.-BH4)(.mu.-H)(CO)5(.mu.-Ph2PCH2PPh2)], a molecule displaying a novel coordination mode of the tetrahydroborate ligand
Reactivity of the unsaturated dihydrides [Mn2(.mu.-H)2(CO)6(.mu.-L2)] (L2 = Ph2PCH2PPh2, (EtO)2POP(OEt)2) toward boron hydrides. X-ray crystal structure of [Mn2(.mu.-BH4)(.mu.-H)(CO)5(.mu.-Ph2PCH2PPh2)], a molecule displaying a novel coordination mode of the tetrahydroborate ligand
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不饱和二氢化物 [Mn2(μ-H)2(CO)6(μ-L2)] (L2 = Ph2PCH2PPh2, (EtO)2POP(OEt)2) 对硼氢化物的反应性。
DOI：
10.1021/om00029a059
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发表时间：
1993
期刊：
影响因子：
2.8
通讯作者：
Y. Jeannin
中科院分区：
文献类型：
--
作者：
R. Carreno;V. Riera;Miguel A. Ruiz;C. Bois;Y. Jeannin
15.735 (2) A，c= 15.960 (1) A，ß= 111.54 (1)，V= 3015.2 (8) A1 23，Z= 4)。对于 4968 次反射，结构被细化为 R= 0.031 (Rv= 0.031)，且 I> 3 ()。四氢硼酸盐配体通过其三个氢原子结合双金属中心，从而在锰原子周围形成扭曲的八面体环境。与Mn(2)的结合是通过H(3)(B-Mn(2)＝2.480A，BH(3)-Mn(2)118.1-(20))以端上方式进行，而与Mn(1)的结合是通过H(2)和H(4)以侧边方式进行(B-Mn(1)＝2.048(4)A，BH-Mn(1)＝分别为 87.9 (16) 和 89.5 (17)）。二氢化锰与“B3H7”在室温下反应得到六羰基和五羰基四氢硼酸盐配合物的混合物，后者是主要产物。最后，在水存在下与 BEt3 反应以良好的产率得到乙氧基配合物 2 (μ-)(μ-OEt)(0) ß (μ-2)，尽管反应途径仍然不清楚。通过使用等瓣关系，将四氢硼酸盐配合物的结构和键合与硼氢化物或金属簇的结构和键合进行比较。
15.735 (2) A, c= 15.960 (1) A, ß= 111.54 (1), V= 3015.2 (8) A1 23, Z= 4). The structure was refined to R= 0.031 (Rv= 0.031) for 4968 reflections with I> 3 (). The tetrahydroborate ligand binds the dimetal center through three of its hydrogen atoms which thus complete distorted octahedral environments around the manganese atoms. Binding to Mn (2) is made in a rather end-on way through H (3)(B-Mn (2)= 2.480 A, BH (3)-Mn (2) 118.1-(20)) whereas binding to Mn (l) is made through H (2) and H (4) in a side-on way (B-Mn (l)= 2.048 (4) A, BH-Mn (l)= 87.9 (16) and 89.5 (17), respectively). Reaction of the manganese dihydrides with “B3H7” at room temperature gave a mixture of the hexacarbonyl and pentacarbonyl tetrahydroborate complexes, the latter as major products. Finally, reaction with BEt3 in the presence of water gave the ethoxy complexes 2 (µ-)(µ-OEt)(0) ß (µ-2) in good yields, although the reaction pathway remains obscure. The structure and bonding in the tetrahydroborate complexes is compared with that of boron hydrides or metal clusters by using isolobal relationships.