SYNTHESIS AND OXIDATIVE ADDITION REACTIONS OF A PHOSPHINE CARBONYL COMPLEX OF OSMIUM (0)
SYNTHESIS AND OXIDATIVE ADDITION REACTIONS OF A PHOSPHINE CARBONYL COMPLEX OF OSMIUM (0)
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DOI：
10.1021/ja00967a007
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发表时间：
1966-01-01
影响因子：
15
通讯作者：
ROPER, WR
中科院分区：
文献类型：
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作者：
COLLMAN, JP;ROPER, WR
第一个锇 (O) 膦络合物 Os (CO) 3 [P (C6H5) 3] 2 是由一类新型锇 (II) 络合物 OsX2 (CO) 2 [P (C6H5) 3] 2 在一氧化碳存在下通过锌还原制备而成。使用三苯膦和仅 60 psi 的一氧化碳压力，由 OsCl3·xH2O 和 (NH4) 2OsBr6 制备锇-(II) 配合物。锇 (O) 络合物表现出与卤化氢反应的基本性质。该反应通过阳离子氢化物中间体进行，生成 OsX2 (CO) 2 [P (C6H6) 3] 2 ，与原始锇 (II) 配合物相同。通过用碘和溴氧化锇 (O) 化合物，生成类似的阳离子络合物，{Os (CO) 3X [P (C6H5) 3] 2}+ X~ 进一步说明了这一基本特征。在溶液中，这些化合物表现为 1:1 电解质，并缓慢地置换 CO，形成原始非离子络合物 OsXítCO^ IPÍCeHsMs。已经对这些配合物进行了立体化学分配。无机化学的快速发展不断出现类似反应的新模式。在某些情况下，无机反应可以通过官能团方法进行系统化，类似于有机化学中长期使用的定性成功方法。此类无机转化涉及氧化加成反应，其中-
The first phosphine complex of osmium (O), Os (CO) 3 [P (C6H5) 3] 2, has been prepared from a new class of osmium (II) complexes, OsX2 (CO) 2 [P (C6H5) 3] 2, by zinc reductionin the presence of carbon monoxide. The osmium-(II) complexes were prepared from OsCl3· xH20 and (NH4) 2OsBr6 using triphenylphosphine and carbon monoxide pressures of only 60 psi. The osmium (O) complex exhibits basic properties as illustrated by its reaction with hydro-gen halides. This reaction proceeds through a cationic hydride intermediate to yield OsX2 (CO) 2 [P (C6H6) 3] 2, identical with the original osmium (II) complexes. This basic character is further illustrated by oxidation of the osmium (O) compound with iodine and bromine to yield similar cationic complexes,{Os (CO) 3X [P (C6H5) 3] 2}+ X~. In solution these compounds behave as 1: 1 electrolytes and slowly undergo displacement of CO to form the original nonionic complexes OsXítCO^ IPÍCeHsMs. Stereochemical assignments have been made for these complexes.New patterns of analogous reactions continue to emerge from the rapid development of inorganic chemistry. In some instances inorganic reactions can be systematized by a functional group approach similar to that long used with qualitative success in organic chemistry. Onesuch class of inorganic trans-formations involves oxidative addition reactions where-