Abstract
Abstract The triphos ligand CH3C(CH2PPh2)3 reacts with Co(BF4)2 (aq) or Fe(BF4)2 (aq) in the presence of nitriles RCN to produce the pentacoordinate [triphosCo(NCR)2](BF4)2 (1) or the hexacoordinate [triphosFe(NCR)3](BF4)2 (2). With α,ω-dinitriles NC-X-CN dinuclear compounds [triphosFe(NC-X-CN)3Fetriphos](BF4)4 (X = (CH2)3 (3a) X = o-C6H4 (3b) are formed. The compound [triphosFe((CH3)2C=C(CN)2)3Fetriphos](PF6)4 (3c) is obtained from FeCl2 by addition of the triphos ligand, the dinitrile and NaPF6. All compounds are characterised by the usual analytical techniques including X-ray analyses. It is observed that the quadruply positively charged compounds 3 tend to associate the respective anions in pockets formed by the three segments of the Fe(NC-X-CN)3Fe bridg ing units.
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