Photochemistry of some bis(metal carbonyl) germanes and (metal carbonyl)chlorogermanes. Formation of germanium-bridged metal-metal bonds

[BMIm]2[Mn(CO)3(GeI3)3]: Carbonyl Compound with an {MnGe3} Cluster Unit

“…16 Finally, it needs to be noticed that several of the aforementioned compounds with Ge−Mn bonding were reported only with limited characterization (e.g., elemental analysis or vibrational spectroscopy only), yet without profound structural characterization. 3,4,[7][8][9][10]12,17,18 With our studies on the reactivity of metal carbonyls in ionic liquids, we have already demonstrated the synthesis of compounds with group 14 elements and transition metal carbonyls. Specifically, this includes the systems Ge−Fe, Sn− Fe, and Pb−Mn and results in compounds such as the cluster [Ge 12 {Fe(CO) 3 } 8 (μ-I) 4 ], which is based on a {Ge 12 Fe 8 } cluster core, 11 the cluster anion [{Fe(CO) 3 } 4 {SnI} 6 I 4 ] 2− comprising an adamantane-type {Fe 4 Sn 6 } unit, 12 20 For these syntheses, ionic liquids turned out to be ideal reaction media due to their specific features, such as high redox stability and weakly coordinating properties.…”

“…Manganese–germanium carbonyls and Mn–Ge bonding in clusters were intensely studied in regard of structure and reactivity in the 1970s and 1980s. − Predominately, diatomic species [X 3 Ge–Mn­(CO) 5 ] (X: Cl, Br, H, CH 3 ) were realized. Moreover, {Ge–Mn–Ge} or {Mn–Ge–Mn} strings, such as in [Et 4 N]­[Mn­(CO) 4 {GePh 3 } 2 ], [Et 4 N]­[Mn­(CO) 4 {Ge­(CH 3 ) 3 } 2 ], [(GeCl 3 ) 2 Mn­(CO) 2 Cp], [{Cp′(CO) 2 Mn} 2 Ge­(Bipy)], [GeMe 2 Mn­(CO) 9 ], and [(GeMe 2 ) 2 {Mn­(CO) 4 } 2 ], were realized. Larger arrangements containing more than three Ge/Mn atoms are rare and limited to {Ge 2 Mn 2 } rings like in [(GeMe 2 ) 2 {Mn­(CO) 4 } 2 ] or [(LGe)­μ-{Mn­(CO) 4 }] 2 (L: 2-imino-5,6-methylene­dioxylphenyl) .…”

Photochemical Route to Actinide-Transition Metal Bonds: Synthesis, Characterization and Reactivity of a Series of Thorium and Uranium Heterobimetallic Complexes

“…Formation of metal-metal bonds by this route is unusual for transition metals and, to our knowledge, has never been seen for actinides. [39][40][41] Subjecting the isolated compounds 4 4 and 5 5 to subsequent irradiation under the same conditions does not result in further carbonyl ligand substitution. Additionally, 6 6 and 7 7 do not react with CO under either thermal or photochemical conditions to reform 4 4 and 5 5.…”

The reactions of methylgermanes with [µ4-Ge{Co2(CO)7}2]: extending the chain of linked GeCo2triangles

“…When the 13C0 NMR spectra were run, the ',CO enriched sample of 2b gave a singlet at 6 199.8 at -50 "C, and at 6 202.5 at -5 "C; 1 showed a singlet at 6 201.9 at room temperature and at -50 "C. The mass spectrum of 2b showed a relatively weak parent ion and all members of the ( P -nCO)+ series from n = 0 to 13. Relative intensities were 17,14,17,25,23,34,100,93,57,23,42,51,39 and 77% for n = 0 to 13 respectively. The much weaker series ( P -nCO -CH,)+ occurred with only l-lO% of these intensities apart from n = 3 and 2 (20) and n = 0 (73%).…”