Interesting synthetic routes from the reinvestigation of the reaction of the M(CO)6 (M=Cr, Mo and W) species with KOH

Assembling Process of Charged Nonanuclear Cationic Lanthanide(III) Clusters Assisted by Dichromium Decacarbonyl Hydride

“…On the other hand particular attention has been paid, in these last years, also to the isolation of heteronuclear compounds produced by reaction of lanthanide complexes with transition metal carbonyls for applications of such systems in selective catalytic processes . With the aim to provide new heteronuclear chromium carbonyl lanthanide complexes we have studied the reaction of the lanthanide tris-2,4-pentadionates, Ln(acac) 3 ·3H 2 O (Ln = Sm, Eu, Gd, Dy and Yb), with the dichromium decacarbonyl hydride, [Cr 2 (CO) 10 (μ-H)] - , where dichromium decacarbonyl hydride should act as reducing agent by oxidation of the hydridic hydrogen . This system evidenced the formation, under mild conditions, of a series of polynuclear compounds as prevalent reaction products of general formula [Ln 9 (acac) 16 (OH) 10 ] + [Cr 2 (CO) 10 (μ-H)] - (Ln = Sm (1a) , Eu (1b) , Gd (1c) , Dy (1d) , Yb (1e) ) as deduced by X-ray analysis and chemical data (see below).…”

Synthesis and X-ray crystal structure of cationic polynuclear hydroxide acetylacetonate lanthanide(III) clusters with homodinuclear or heterodinuclear decacarbonyl hydrides: [HMo2(CO)10]− and [HCrW(CO)10]−

“…All the new species show the characteristic hydroxide sharp band around 3570 cm −1 and a broad band in the range 3340-3350 cm −1 , respectively, assigned to the 4 OH and 3 OH stretching modes [27,28]. Table 4 FTIR data (cm −1 ), nujol mulls, for (1a-e) and complex (2a) 3576w 3339b 2033w 1942s 1905w 1869s 1618s 1589s 1514s 1257m 1016m 922m 656w 594w 1b 3578w 3337b 2033w 1944s 1905w 1869s 1618s 1589s 1522s 1259m 1016m 922m 658w 594w 1c 3577w 3339b 2035w 1944s 1905w 1871s 1622s 1595s 1522s 1265m 1020m 922m 656w 592w 1d 3566w 3350b 2033w 1944s 1905w 1870s 1618s 1595s 1518s 1261m 1020m 924m 658w 592w 1e 3587w 3339b 2035w 1944s 1905w 1871s 1622s 1595s 1522s 1265m 1018m 926m 661w 594w 2a 3576w 3346b 2033w 1940s -1869s 1618s 1591s 1522s 1258m 1016m 922m 663w 598w s, strong; m, medium; w, weak; b, broad.…”

Pentacarbonylhydridochromates M+[HCr(CO)5]−: Reactivity in Organic Synthesis and Homogeneous Catalysis

“…Both the water content and the temperature are important factors. [26] More recently, a rapid and useful preparation of [K] ϩ [HCr(CO) 5 ] Ϫ has been reported, which is carried out in a CH 2 Cl 2 /EtOH solvent mixture at room temperature [Equation (10)]. [27] The advantages of this procedure are its high reproducibility (70Ϫ78% yield from each of 30 runs) and the fact that only 2 equiv.…”

“…[48] These conclusions are relevant to the recent observation that, in contrast to the [PPN] ϩ salt, the potassium salt [K] ϩ [HCr(CO) 5 ] Ϫ does react with cyclohexanone in the absence of acid. [49] The stoichiometric reaction of [K] ϩ [HCr(CO) 5 ] Ϫ with cyclohexanone at room temperature in THF leads, after hydrolysis, to cyclohexanol (50% yield, 24 h) [Equation (26)]. (26) However, the yield could not be increased by using longer reaction times (120 h).…”

“…[49] The stoichiometric reaction of [K] ϩ [HCr(CO) 5 ] Ϫ with cyclohexanone at room temperature in THF leads, after hydrolysis, to cyclohexanol (50% yield, 24 h) [Equation (26)]. (26) However, the yield could not be increased by using longer reaction times (120 h). Spectroscopic analysis of the reaction medium prior to hydrolysis indicated that free cyclohexanol was already present.…”