Syntheses, Crystal Structures, and Properties of Novel Heterooctametallic Clusters Na2M'2[M3O4(O2CEt)8]2 (M' = Fe, Cr, Mo; M3 = Mo3, MoW2, W3)

✍ Scribed by Li Xu; Zhaohui Li; Huang Liu; Jinshun Huang; Qianer Zhang

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 628 KB
• Volume: 3
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/chem.19970030210

✦ Synopsis

A mixture of Na,MO,, M(CO),, FeC1,.6 H,O, and (EtCO),O was heated at 120 ' C to produce the heterooctanuclear clusters Na,Fe,[M,O,-(O,CEt),], (M = Mo, 1; W, 2). The bioxo-capped clusters Na[M,O,(O,CEt),] (M, = MOW,, W,) were treated with Fe-(CO),, Cr(CO),, and Mo(CO), in (EtCO),O at 120°C to afford Na,M',-[MoW,O,(O,CEt),], (M' = Fe, 3; Cr, 4; Mo, 5) and Na,Mo,[W,O,(O,CEt),], (6), respectively. The isomorphous clusters 1, 2, 5, and 6 were characterized by X-ray crystallography. The structures, similar to those o f the analogues Nd,Cr,[M,O,-(O,CEt),] (M = Mo, 7; W, 8) and Na,V,[M,O,(O,CEt),], (M = Mo, 9; W, lo), consist of two incomplete cubanetype [M,0,(0,Et),]4-units centrosymmetrically bridged by two M'(III) metal ions through p o x 0 and propionate groups; the resulting cluster dianions are linked by Na' ions into infinite chains. Clusters 1-10 do not dissolve in water and common organic solvents at room temperature. Unlike the chromium(lI1) clusters 7 and 8, the iron(ri1) and vanadium(iri) clusters 1 and 9 are soluble in Keywords chromium * clustersiron * molybdenum * tungsten