Synthesis and characterisation of HRuRh3(CO)12. Crystal structures of HRuRh3(CO)12, HRuRh3(CO)10(PPh3)2 and HRuCo3(CO)10(PPh3)2

Reactivity of the Heterometallic Clusters [HMCo3(CO)12] and [Et4N][MCo3(CO)12] (M = Fe, Ru) toward Phosphine Selenides, Including Selenium Transfer. Crystal Structures of [HRuCo3(CO)7(μ-CO)3(μ-dppy)], [MCo2(μ3-Se)(CO)7(μ-dppy)], and [RuCo2(μ3-Se)(CO)7(μ-dppm)] [dppy = Ph2(2-C5H4N)P, dppm = Ph2PCH2PPh<

“…The solid-state structures for 17 and 3 have already been reported in the literature by Hidai et al and Pakkanen et al . along with their spectroscopic data in solution.…”

“…In compounds [HRuCo 3 (CO) 7 (μ-CO) 3 (PPh 3 ) 2 ] ( 4 ) and [HFeCo 3 (CO) 7 (μ-CO) 3 (dppyth) 2 ] ( 20 ), two carbonyl groups have been substituted by two monodentate phosphines (Schemes , ); they have been identified by comparison of their spectroscopic data (IR, 1 H NMR, color, elution order on TLC) with those found in the literature. , In particular, compound 4 is supposed to be the Ru, Co isomer on the basis of the sharp hydride signal in the 1 H NMR spectrum at δ = −17.8.…”

“…Thus, the presence of different metals, which provides a larger diversity of possible coordination sites, can influence the selectivity of certain processes and lead to the formation of compounds presenting new and not always easily predictable geometries. The reactivity of tetrahedral clusters of the type [HMCo 3 (CO) 12 ] (M = Ru and Fe) with nucleophiles (especially tertiary phosphines, phosphites, amines) generally leads to a metallosite-selective substitution of one or more carbonyl ligands (on the basal plane). − The first substitution by donor ligands generally occurs by replacement of a terminal axial carbonyl of a cobalt atom. A recent exception was observed in the reaction of [HMCo 3 (CO) 12 ] with PCyH 2 which led to CO substitution at the apical Ru center .…”

“…A recent exception was observed in the reaction of [HMCo 3 (CO) 12 ] with PCyH 2 which led to CO substitution at the apical Ru center . On the contrary, the introduction of a second ligand can take place either on a basal or on the apical metal. − ,− , The effects of phosphine substitution on the other ligands are usually restricted to minor distortions, for example, asymmetry in the carbonyl coordination; rarely is the position of the hydride ligand also affected. −,− …”

Unexpected Metallosite-Selective CO Substitution of Heteronuclear Tetrahedral (μ3-S)FeCoM (M = Mo, W) Carbonyl Clusters with Cyclohexyl Isocyanide: 59Co NMR and 57Fe Mössbauer Spectra of (μ3-S)FeCoMo(CO)8-n(η5-C5H4COMe)(C6H11NC)n (n = 1−3) and Crystal Structures of (μ3-S)FeCoM(CO)8-n(η5Song1, Luo2, Hu3 et al. 2001Organometallics6000View full textAdd to dashboardCite

“…It is known that the study on metallosite selectivity in carbonyl substitution of heteronuclear tetrahedral clusters is of considerable interest and has shown that the selectivity could be influenced by several factors, such as the nature of the metals in clusters, the type of both existing and attacking ligands, etc. For example, (i) while clusters HMCo 3 (CO) 12 (M = Fe, Ru) react with primary phosphine PCyH 2 (Cy = cyclohexyl) to give monosubstituted products in which PCyH 2 is bonded respectively to Co or Ru, they react with secondary and tertiary phosphines to afford monosubstituted derivatives in which the phosphine ligand is always bonded to Co; − (ii) while HRuCo 3 (CO) 12 reacts with Me 2 Te to yield a monosubstituted product in which Me 2 Te is bonded to Ru, HRuRh 3 (CO) 12 reacts with PR 3 to produce monosubstituted derivatives in which PR 3 is attached to Rh; (iii) in the disubstituted product HRuCo 3 (CO) 10 (PMe 2 Ph) 2 the second PMe 2 Ph is substituted at Ru, whereas in HRuCo 3 (CO) 10 (PPh 3 ) 2 each PPh 3 is bonded to Co; (iv) while trisubstitution of HFeCo 3 (CO) 12 with P(OMe) 3 occurs at each axial site of the three Co atoms, that of HFeCo 3 (CO) 12 with PMe 2 Ph or HRuCo 3 (CO) 12 with various phosphines affords products in which the third ligand is attached to Fe 9 or Ru, respectively.…”