Reactivity of a Base-Stabilized Germanium(I) Dimer toward Group 9 Metal(I) Chloride and Dimanganese Decacarbonyl

Abstract

The reactivity of the 2-imino-5,6-methylenedioxylphenylgermanium(I) dimer toward group 9 metal(I) chloride and dimanganese decacarbonyl is described. [LGe:] (1, L = 2-imino-5,6-methylenedioxylphenyl) underwent a disproportionation reaction with 1.5 equiv of group 9 metal(I) chloride [MCl(cod)] (M = Rh, Ir) in toluene to afford a mixture of the group 9 metallogermylene-chlorometal(I) complexes [LGeμ-{M(cod)}Cl] (M = Rh (2), Ir (4)) and chlorogermylene-chlorometal(I) complexes [L(Cl)GeM(cod)Cl] (M = Rh (3), Ir (5)), respectively. The disproportionation property of 1 is further evidenced by its reaction with 0.5 equiv of Mn(CO) in refluxing toluene to form a mixture of the manganogermylene dimer [(LGe)μ-{Mn(CO)}] (7) and free ligand [LH] (8). Compounds 2-5, 7, and 8 were elucidated by NMR spectroscopy, X-ray crystallography, and DFT calculations, respectively.

Electrochemical and Reactivity Studies of N→Sn Coordinated Distannynes

“…Recently, So et al. also showed that N→Ge coordinated digermyne behaved as a σ donor toward [{M(cod)Cl} 2 ] (M=Ir, Rh) and dimanganese decacarbonyl [Mn 2 (CO) 10 ] …”

“…Compounds 1-3 and 7 were prepared according to reports in the literature, [10,12] and TEMPO and [Fe(CO) 5 ]w ere purchased from Sigma Aldrich. The 1 H, 13 Ca nd 119 Sn NMR spectra were recorded on aBruker Avance500 spectrometer at 300 Ki nC 6 D 6 .C hemical shifts (d)a re given in ppm and referenced to external Me 4 Si and Me 4 Sn. Elemental analyses were performed on an LECO-CHNS-932 analyser.I Rs pectra were recorded on aN icolet 6700 FTIR spectrometer by using as ingle-bounce silicon attenuated total reflectance (ATR) crystal (resolution 2cm À1 ).…”

“…Ge coordinated digermyne behaved as a s donort oward [{M(cod)Cl} 2 ]( M = Ir,R h) and dimanganese decacarbonyl [Mn 2 (CO) 10 ]. [13] CV measurements of 1-5…”

“…In this field, So et al. showed the possible coordination of N→Ge coordinated digermyne to Group 9 metal(I) chlorides [{M(cod)Cl} 2 ] (M=Ir, Rh; cod=1,5‐cyclooctadiene) and dimanganese decacarbonyl [Mn 2 (CO) 10 ] . According to Pearson's theory, distannynes may be considered as soft bases; thus, the use of soft acids, such as [Fe(CO) 5 ], is the easiest method to form the Sn I →TM bond.…”

“…In this field, So et al showedt he possible coordinationo f N!Ge coordinated digermyne to Group 9m etal(I) chlorides [{M(cod)Cl} 2 ]( M = Ir,R h; cod = 1,5-cyclooctadiene)a nd dimanganese decacarbonyl [Mn 2 (CO) 10 ]. [13] According to Pearson's theory,d istannynes may be considered as soft bases; thus,t he use of soft acids,s uch as [Fe(CO) 5 ], is the easiest method to form the Sn I !TM bond. Therefore, compounds [{L 1 Sn} 2 ·Fe(CO) 4 ]( 4)a nd [{L 2 Sn} 2 ·Fe(CO) 4 ]( 5)w ere prepared, and the redox potentials of tin atoms in 4 and 5 were measured to determine the influence of Sn I !Fe coordination.C V measurements of 1-5 were performed, and the oxidation potentials of the tin atom were determined.…”