SYSTEMATIC AND EFFICIENT SYNTHESES OF RU6(CO)182-, RU6C(CO)162-, OS6(CO)182-, AND OS10C(CO)242-. ISOLATION AND CHARACTERIZATION OF OS6C(CO)17
SYSTEMATIC AND EFFICIENT SYNTHESES OF RU6(CO)182-, RU6C(CO)162-, OS6(CO)182-, AND OS10C(CO)242-. ISOLATION AND CHARACTERIZATION OF OS6C(CO)17
复制标题
RU6(CO)182-、RU6C(CO)162-、OS6(CO)182- 和 OS10C(CO)242- 的系统高效合成。
DOI：
10.1002/chin.198252310
复制
发表时间：
1982
期刊：
影响因子：
--
通讯作者：
J. Shapley
中科院分区：
文献类型：
--
作者：
C. T. Hayward;J. Shapley
Ru_3(CO)_(12)或Os_3(CO)_(12)在不同反应温度的乙醚溶剂中与钠反应，可以有效地制备出几个大的Ru和Os3(CO)_12的阴离子羰基簇合物。Ru_3(CO)_(12)与1当量钠(Ru_3：Na=1：1)在回流四氢呋喃(66℃)中得到Ru6(CO)182“，而在回流二醛(162 C)中得到Ru_6C(CO)162”。在后一种条件下，Ru6(CO)182“被定量地转化为Ru6C(CO)162~.在162℃下，OS3(CO)12与(OS3：Na=1：1)铟缩合生成OS6(CO)182”.OS6(CO)182“在三甘醇(216℃)中热解，主要产物为Os10C(CO)242”。十核化合物也是由OS3(CO)12与钠(OS3：Na=1.66：1或1：1)在四甘醇中在230-260℃下直接反应生成的。在一氧化碳气氛中，Ru、C(CO)162“和OS6(CO)182”与三氯化铁水溶液在一氧化碳气氛中氧化生成Ru6C(CO)17和OS6(CO)18。从OS6(CO)182“热解产生的反应混合物的类似氧化反应中低产率地分离出一种化合物，命名为Os6C(CO)17，这是在OS6(CO)182”转化为Os10C(CO)242“的条件下生成Os6C(CO)162”的证据。
Treatment of Ru3 (CO) 12 or Os3 (CO) 12 with sodium in ether solvents at various reaction temperatures provides efficient preparations of several large anionic carbonyl clusters of ruthenium and osmium. The combinationof Ru3 (CO) 12 and 1 equiv of sodium (Ru3: Na= 1: 1) affords Ru6 (CO) 182" in refluxing tetrahydrofuran (66 C) but Ru6C (CO) 162" inrefluxing diglyme (162 C). Under the latter conditionsRu6 (CO) 182" is converted quantitatively to Ru6C (CO) 162~. Treatmentof Os3 (CO) 12 with sodium (Os3: Na= 1: 1) indiglyme at 162 C yields Os6 (CO) 182". Pyrolysis of Os6 (CO) 182" in triglyme (216 C) gives Os10C (CO) 242" as the major product. The decanuclear compound also is formed from the direct reaction of Os3 (CO) 12 with sodium (Os3: Na= 1.66: 1 or 1: 1) in tetraglyme at 230-260 C. Oxidation of Ru€ C (CO) 162" and Os6 (CO) 182" with aqueous ferric chloride in a carbon monoxide atmosphere produces Ru6C (CO) 17 and Os6 (CO) 18 in good yields. A compound formulated as Os6C (CO) 17 is isolated in low yield from the similar oxidation of reaction mixturesproduced upon pyrolysis of Os6 (CO) 182". This is suggested as evidence for the formation of Os6C (CO) 162" under the conditions for conversion of Os6 (CO) 182" to Os10C (CO) 242".