Pentamethylcyclopentadienyl-rhodium and -iridium complexes. Part 29. Syntheses and X-ray structure determinations of [{Rh(C5Me5)}2(OH)3]OH·11H2O and [{lr(C5Me5)}2(OH)3]O2CMe·14H2O and related complexes
Pentamethylcyclopentadienyl-rhodium and -iridium complexes. Part 29. Syntheses and X-ray structure determinations of [{Rh(C5Me5)}2(OH)3]OH·11H2O and [{lr(C5Me5)}2(OH)3]O2CMe·14H2O and related complexes
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五甲基环戊二烯基铑和铱络合物。第 29 部分。[{Rh(C5Me5)}2(OH)3]OH·11H2O 和 [{lr(C5Me5)}2(OH)3]O2CMe 的合成和 X 射线结构测定。 ·14H2O及相关配合物
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发表时间：
1981
期刊：
影响因子：
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通讯作者：
P. Maitlis
中科院分区：
文献类型：
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作者：
A. Nutton;P. M. Bailey;P. Maitlis
合成了配合物[{M（C5 H5）}2（OH）3]X·nH 2 O（M = Rh，X = PF 6和OH; M = Ir，X = O2 CMe，OH和BPh 4）。用X射线单晶衍射法测定了[{Rh（C_5Me_5）}_2（OH）_3]OH·11H_2O（2c）和[{Ir（C_5Me_5）}_2（OH）_3] O_2CMe·14H_2O（3a）的晶体结构。两者都显示出两个金属原子，每个金属原子η5-键合到C5 Me 5配体上，并通过三个羟基配体桥接，其中Rh = Rh 2.973 8（8）A，Ir = Ir 3.070 9（7）A，Rh-O（平均值）2.109 A，Ir-O（平均值）2.120 A，Rh-O-Rh（平均值）89.6（1）°和Ir-O-Ir（平均值）92.8（3）°。（2c）和[{lr（C5 Me 5）}2（OH）3]OH·nH 2 O在水中都是很强的碱。[{Rh（C5 Me 5）} 2Cl 4]（1）与Ag 2SO 4反应生成Rh（C5 Me 5）（SO 4）·2 H2O，其可能以二价阳离子[Rh（C5 Me 5）（H2O）3]2+存在于水中，并定量羰基化（20 °C，1atm，48 h）为[Rh（C5 Me 5）（CO）2]。由（1）与Ag_2CO_3或[{Rh（C_5Me_5）}_2（CO）_2]空气氧化得到碳酸根配合物Rh（C_5Me_5）（CO_3）·2H_2O。[{Rh（C5 Me 5）}2（OH）3]Cl与P（OMe）3反应，得到未预料到的甲基铑配合物[Rh（C5 Me 5）Me{P（OMe）3}2]+和[Rh（C5 Me 5）{P（OMe）3}3]2+。
The complexes [{M(C5H5)}2(OH)3]X·nH2O (M = Rh, X = PF6 and OH; M = Ir, X = O2CMe, OH, and BPh4) have been prepared. Single-crystal X-ray structure determinations have been carried out on [{Rh(C5Me5)}2(OH)3]OH·11H2O (2c) and on [{Ir(C5Me5)}2(OH)3]O2CMe·14H2O (3a). Both show two metal atoms each η5-bonded to a C5Me5 ligand and bridged by three hydroxo-ligands with Rh ⋯ Rh 2.973 8(8)A, Ir ⋯ Ir 3.070 9(7)A, Rh–O (mean) 2.109 A, Ir–O (mean) 2.120 A, Rh–O–Rh (mean) 89.6(1)°, and Ir–O–Ir (mean) 92.8(3)°. Both (2c) and [{lr(C5Me5)}2(OH)3]OH·nH2O are very strong bases in water. Reaction of [{Rh(C5Me5)}2Cl4](1) with Ag2SO4 gave Rh(C5Me5)(SO4)·2H2O which probably exists in water as the dication [Rh(C5Me5)(H2O)3]2+ and which is quantitatively carbonylated (20 °C, 1 atm, 48 h) to [Rh(C5Me5)(CO)2]. The carbonato-complex Rh(C5Me5)(CO3)·2H2O was obtained from (1) and Ag2CO3 or by air-oxidation of [{Rh(C5Me5)}2(CO)2]. Reaction of [{Rh(C5Me5)}2(OH)3]Cl with P(OMe)3 gave the unexpected methylrhodium complex [Rh(C5Me5)Me{P(OMe)3}2]+ as well as [Rh(C5Me5){P(OMe)3}3]2+.