Synthesis and chemical characterization of platinum carbonyl dianions [Pt3(CO)6]n2- (n = .apprx.10,6,5,4,3,2,1). A new series of inorganic oligomers
Synthesis and chemical characterization of platinum carbonyl dianions [Pt3(CO)6]n2- (n = .apprx.10,6,5,4,3,2,1). A new series of inorganic oligomers
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DOI：
10.1021/ja00439a020
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发表时间：
1976-10
影响因子：
15
通讯作者：
G. Longoni;P. Chini
中科院分区：
文献类型：
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作者：
G. Longoni;P. Chini
在碱存在下，在一氧化碳（25 ℃，1大气压）下还原Na_2 PtCl_6·6 H_2 O或Pt（CO）_2Cl_2得到二价阴离子[Pt_3（CO）_6] n_2-（=~ 10，5，4，3），其中n取决于碱：Pt比率。这一系列的其他成员（= 6，2，1）是从预形成的[PtsfCOp] 1，2，2 ″ ″（n = 10，5，4，3）开始通过用锂金属（= 2，1）和钠-钾合金（n= 1）还原或通过用Pt（IV）（= 6）氧化而获得的。这些最后的制备和金属键在n相差大于等于10（n< 6，An> 2）的低聚物之间的重新分布指出了这些化合物改变核性的容易性。增加n降低了对亲电试剂和氧化剂的反应性，同时，对亲核试剂和还原剂的反应性增加。报道了羰基铂催化加氢反应的第一个实例。讨论了这些二价阴离子的主要成键特征，以及类似的镍、钯和铂羰基化合物的不同稳定性。我们对含叔膦和一氧化碳配体的铂（O）簇化学的兴趣促使我们研究了二羰基铂[Pt（CO）2] n的性质和反应性。[5]这种化合物首先由Booth和Chatt分离出来，由于它完全不溶，还没有得到充分的鉴定。我们研究的出发点是观察到二羰基铂在氨水存在下溶解于丙酮中，得到暗绿色的未表征溶液。5
Reduction of Na2PtCl6'6H20 or Pt (CO) 2Cl2 under carbon monoxide (25 C, 1 atm) in the presence of alkali gives the dianions [Pt3 (CO) 6] n2-(=~ 10, 5, 4, 3) where n depends on the alkali: Pt ratio. Other members of this series (= 6, 2, 1) have been obtained starting from preformed [PtsfCOp],, 2""(«= 10, 5, 4, 3) byreduction with lithium metal (= 2, 1) and sodium-potassium alloy (n= 1) or by oxidationwith Pt (IV)(= 6). These last preparations and the redistributionof metal bonds between oligomerswhich differ in n by to or more(n< 6, An> 2) point out the ease with which these compounds change nuclearity. Increasing n decreases the reactivity towards electrophilesand oxidizing agents and, at the same time, the reactivity towards nucleophilesand reducing agents increases. The first example of a platinum carbonyl catalyzed hydroformylation reaction is reported. The main bonding features of these dianions, and the different stabilities of analogous nickel, pal-ladium, and platinum carbonylcompounds, are discussed.Our interest in the chemistry of the platinum (O) clusters containing tertiary phosphinesand carbon monoxide as li-gands2" 4 prompted us to investigate thenature and the reac-tivity of the platinumdicarbonyl,[Pt (CO) 2]„. 5 This compound, which was first isolated by Booth and Chatt, has not been sufficiently characterizedowing to its complete insolubility. The starting point of our research has been the observation that platinumdicarbonyl dissolves in acetone in thepresence of aqueous ammonia to give dark green uncharacterized solutions. 5