Preparation and interconversion of dimeric di-µ-hydroxo and tri-µ-hydroxo complexes of platinum(II) and palladium(II) with 2,2′-bipyridine and 1,10-phenanthroline
Preparation and interconversion of dimeric di-µ-hydroxo and tri-µ-hydroxo complexes of platinum(II) and palladium(II) with 2,2′-bipyridine and 1,10-phenanthroline
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铂(II)和钯(II)与2,2-联吡啶和1,10-菲咯啉的二聚二-μ-羟基和三-μ-羟基络合物的制备和互变
DOI：
10.1039/dt9890000403
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发表时间：
1989
期刊：
影响因子：
--
通讯作者：
N. Johnson
中科院分区：
文献类型：
--
作者：
S. Wimmer;P. Castan;F. Wimmer;N. Johnson
在丙酮中用 AgNO3 处理 [Pt(L)I2][L = 2,2′-联吡啶 (bipy) 或 1,10-菲咯啉 (phen)] 得到硝基配合物 [PtL(ONO2)2]。钯类似物由 [Pd(L)Cl2] 在稀硝酸中制备。 [ML(ONO2)2](M = Pd 或 Pt) 在水中的溶解导致羟基桥联二聚体 [LM(μ-OH)2ML][NO3]2 加硝酸的形成。 [M(L)Cl2] 与 AgNO3 在水中反应，直接得到 [LM(μ-OH)2ML][NO3]2 作为唯一产物。尽管在硝酸水溶液重整中长时间加热，二聚体仍能抵抗取代[ML(ONO2)2]。二聚体添加 1 mol OH– 形成非常稳定的三羟基桥化合物 [LM(μ-OH)3ML]+（M = Pt，深红色；M = Pd，深黄色），其中每种金属都是五配位的。这些络合物被氢氧化物缓慢裂解，得到 [ML(OH)2]，它也可以通过碱水解或 [M(L)Cl2] 与 Ag2O 反应制备。将 HX（X = NO3 或 ClO4）添加到 [PtL(OH)2] 中，分别在 pH 8、4 和 1 下得到 [LPt(μ-OH)3PtL]+、[LPt(μ-OH)2PtL]2+ 或 [PtL(ONO2)2]。该配合物已通过红外、紫外和核磁共振进行了表征。 （195Pt、13C 和 1H）光谱。
Treatment of [Pt(L)I2][L = 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen)] with AgNO3 in acetone gives the nitrato complexes [PtL(ONO2)2]. The palladium analogues were prepared from [Pd(L)Cl2] in dilute nitric acid. Dissolution of [ML(ONO2)2](M = Pd or Pt) in water results in the formation of the hydroxo-bridged dimers [LM(µ-OH)2ML][NO3]2 plus nitric acid. Reaction of [M(L)Cl2] with AgNO3 in water gives [LM(µ-OH)2ML][NO3]2 directly as the sole product. The dimers are resistant to substitution, although prolonged heating in aqueous nitric acid reforms [ML(ONO2)2]. The dimers add 1 mol of OH– to form the very stable trihydroxo-bridged compounds [LM(µ-OH)3ML]+(M = Pt, deep red; M = Pd, deep yellow) where each metal is five-co-ordinate. These complexes are slowly cleaved by hydroxide to give [ML(OH)2], which was also prepared either by base hydrolysis or by reaction of [M(L)Cl2] with Ag2O. Addition of HX (X = NO3, or ClO4) to [PtL(OH)2] affords [LPt(µ-OH)3PtL]+, [LPt(µ-OH)2PtL]2+ or [PtL(ONO2)2] at pH 8, 4, and 1 respectively. The complexes have been characterised by i.r., u.v., and n.m.r. (195Pt, 13C, and 1H) spectroscopy.