Surface‐Assisted Synthesis and Behavior of Dimetallic Mixed‐Metal Complexes [M₂Cl₂(μ‐Cl)₄(CO)₆M′(L)₂] (M = Ru, Os; M′ = Fe, Co; L = CH₃CH₂OH, H₂O)

Abstract

The reductive carbonylation of ruthenium and osmium halides in the presence of cobalt and iron surfaces was studied. In these surface-assisted reactions the metal surface plays an active role in releasing metal ions, which can be used for the in situ synthesis of mixed-metal compounds. A linear, dimetallic, chlorido-bridged, trinuclear complex [Ru 2 Cl 2 (µ-Cl) 4 -(CO) 6 Co(CH 3 CH 2 OH) 2 ] was obtained by the interaction between reducing RuCl 3 and the cobalt surface. In the reaction the RuCl 3 is reduced with carbon monoxide in the presence of a solid cobalt surface in ethanol solution. During the reduction of the RuCl 3 the cobalt surface was simultaneously corroded, releasing cobalt cations. In addition to [Ru 2 Cl 2 (µ-Cl) 4 (CO) 6 Co(CH 3 CH 2 OH) 2 ], the reaction also produced other trinuclear complexes and mononuclear products, such as a bent and linear dimetallic, chlorido-bridged complex with the aqua ligand [Ru 2 Cl 2 (µ-Cl) 4 (CO) 6 Co(H 2 O) 2 ] and ionic

Hexaaquairon(II) bis[fac-tribromidotricarbonylferrate(II)]

“…For the chemistry of FeBr 2 (CO) 4 , see: Hieber & Bader (1928); Robertson et al (2000). For the syntheses and crystal structures of anologous compounds with [(Fe/Co/Ru)(H 2 O) 6 ] 2+ cations and [(Ru/Os)(Cl/I) 3 (CO) 3 ] À complexes, see: Allen (2002); Taimisto et al (2003); Haukka et al (2006); Jakonen et al (2007). Mo K radiation = 12.37 mm À1 T = 100 K 0.26 Â 0.10 Â 0.08 mm…”

One-step synthesis of oxamidato bridged fac-Ru(CO)3 core based dinuclear compounds: Spectroscopic and structural characterisation

“…To ascertain this presumption that the oxamidato bridged dinuclear compounds are formed via iodido bridged intermediate, a control reaction involving Ru 3 (CO) 12 and iodine was carried out in mesitylene at 50 C for 5 h. IR spectrum of the product in dichloromethane displayed three bands at n (CO) 2123 (s), 2067 (vs) and 2011 (w) cm À1 and the pattern was found to be similar to the IR spectra of [X(CO) 3 Ru(m-X) 2 Ru(CO) 3 [55,57]. To this, N,N 0 -dibutyloxamide was added and the reaction was further continued at 130 C for 10 h. The product was isolated as a yellow solid and its IR spectrum was identical to that of butyloxamidato bridged compound [I(CO) 3 Ru(m-dbo) Ru(CO) 3 …”

“…The orange crystals on structural analysis using single crystal X-ray diffraction analysis revealed an iodido bridged dinuclear ruthenium compound [I(CO) 3 Ru(m-I) 2 Ru(CO) 3 I]. Jakonen et al prepared and structurally characterised this iodido bridged compound via reductive carbonylation of RuCl 3 under high pressure of carbon monoxide [55,56]. The structure of iodido bridged compound displayed dinuclear framework in which two fac-Ru(CO) 3 units are associated together via two iodido bridges.…”

“…IR spectra of the compounds 1e3 in CH 2 Cl 2 displayed strong bands in the region of n (CO) 2126À2000 cm À1 characteristic to the facRu(CO) 3 core in an octahedrally coordinated metal centre [55,58]. from n 1650 to 1605 cm À1 and the disappearance of NH stretching bands in compounds 1À3 in comparison to the signals of free ligands H 2 L indicated chelation of oxamide ligands with ruthenium centres.…”

Surface‐Assisted Synthesis and Behavior of Dimetallic Mixed‐Metal Complexes [M2Cl2(μ‐Cl)4(CO)6M′(L)2] (M = Ru, Os; M′ = Fe, Co; L = CH3CH2OH, H2O)

“…The last column in Table 1 on page 3503 of the original article 1 is incorrect. The correct Table 1 and two sentences referring to this table in lines 13–21 of the right‐hand column on the same page are given below.…”