“…Ge–Ge bond length [2.4266(9) vs. 2.4284(6) vs. 2.4316(13) Å in 3c , 4a , 5a , respectively] and Ge–C bond length [for example, Ge–C ArM 1.972(6) vs. 1.970(6) vs. 1.974(9) Å]. Furthermore, the d (Ge–C ArM ) is longer than the other Ge–C bonds; this may be explained as by steric reasons [introduction of a more voluminous M(CO) 3 substituent] and by electronic effects (similar to ones, which have been earlier observed for donor‐acceptor oligogermanes) , . In general, the geometry at each of Ge atom may be described as a slightly distorted tetrahedral.…”
The ligand properties of a series of aryl oligogermanes R3Ge‐GeAr3, 3–7 [Me3Ge‐GePh3 (3), Me3Ge‐Ge(pTol)3 (4), Ph3Ge‐GePh3 (5), (C6F5)3Ge‐GePh3 (6), Ph3Ge‐GeMe2GePh3 (7)] for the synthesis of transition metal carbonyl complexes such as R3Ge‐GeAr2(R′C6H4‐η6)M(CO)3 (M = Cr, 3a–7a; M = Mo, 3b; M = W, 3c) were investigated. The target complexes were obtained in moderate yields using several different synthetic approaches. The physicochemical properties of these new derivatives were investigated by IR, UV/Vis, NMR spectroscopy, electrochemistry, and DFT calculations. The molecular structures of 3c, 4a, and 5a were studied by single‐crystal X‐ray diffraction analysis. A comparative analysis of donor and acceptor properties of aryl oligogermanes as ligands for transition metal carbonyl complexes is reported.
“…Ge–Ge bond length [2.4266(9) vs. 2.4284(6) vs. 2.4316(13) Å in 3c , 4a , 5a , respectively] and Ge–C bond length [for example, Ge–C ArM 1.972(6) vs. 1.970(6) vs. 1.974(9) Å]. Furthermore, the d (Ge–C ArM ) is longer than the other Ge–C bonds; this may be explained as by steric reasons [introduction of a more voluminous M(CO) 3 substituent] and by electronic effects (similar to ones, which have been earlier observed for donor‐acceptor oligogermanes) , . In general, the geometry at each of Ge atom may be described as a slightly distorted tetrahedral.…”
The ligand properties of a series of aryl oligogermanes R3Ge‐GeAr3, 3–7 [Me3Ge‐GePh3 (3), Me3Ge‐Ge(pTol)3 (4), Ph3Ge‐GePh3 (5), (C6F5)3Ge‐GePh3 (6), Ph3Ge‐GeMe2GePh3 (7)] for the synthesis of transition metal carbonyl complexes such as R3Ge‐GeAr2(R′C6H4‐η6)M(CO)3 (M = Cr, 3a–7a; M = Mo, 3b; M = W, 3c) were investigated. The target complexes were obtained in moderate yields using several different synthetic approaches. The physicochemical properties of these new derivatives were investigated by IR, UV/Vis, NMR spectroscopy, electrochemistry, and DFT calculations. The molecular structures of 3c, 4a, and 5a were studied by single‐crystal X‐ray diffraction analysis. A comparative analysis of donor and acceptor properties of aryl oligogermanes as ligands for transition metal carbonyl complexes is reported.
“…Furthermore, this method has been limited by the compatibility of some of the initial reagents. For instance, it is impossible to use geminal polyamides, R2Ge[NMe2]2, to construct the Ge-Ge bond [13] . Although the corresponding vicinal diamides, Me2NGePh2GePh2NMe2 [14] , and branched monoamides, [Ph3Ge]3GeNMe2 [15] , are known and are sufficiently stable to be used under hydrogermolysis conditions, there is no data in the literature on using linear catenated germylmonoamide and their application in Ge-Ge bond formation.…”
Section: Scheme 1 General Methods For Creation the Ge-ge Bondmentioning
confidence: 99%
“…It was previously established that the physical properties of the oligogermanes highly depend on the nature of the substituent, on their geometrical volume, on the number of Ge atoms in the chain and on the overall conformation of the molecule. Thus, the introduction of donating groups destabilize the HOMO [16] level, whereas the presence of withdrawing groups resulted in a stabilization of the LUMO [10,13] , by improving the σ-conjugation. The same effect is observed when the Ge chain is elongated.…”
Section: Scheme 1 General Methods For Creation the Ge-ge Bondmentioning
confidence: 99%
“…Compounds 3 and 4 were isolated as white air-and moisture stable powders in high yields (78 and 84 %, respectively). The structure of these compounds in solution was confirmed by multinuclear NMR spectroscopy ( 1 H, 13 C, 19 F) and their composition was established on the basis of elemental analysis. In general, 1 H and 13 C NMR spectra for both compounds are very similar.…”
Section: Scheme 2 Synthetic Strategy For the Synthesis Of Catenated mentioning
confidence: 99%
“…1, 3; Supporting Information, Table S1). Up todayonly 12 linear molecular trigermanes have been studied by XRD (for details see [13] ), where Ge-Ge bond length and Ge-Ge-Ge angle vary between 2.413-2.6223 Å and 110.4-125.00 o , respectively, depending on the steric size and on the electronic nature of the substituents located at Ge atoms. Compound 3 crystallizes in the P-1 space group (Z = 2).…”
The linear oligogermyl amide 2, Ph3GeGeMe2NMe2, was obtained by reacting Ph3GeLi with 1, Me2Ge(Cl)NMe2. The amide 2 was used for the synthesis of molecular oligogermanes 3, Ph3GeGeMe2Ge(C6F5)3, and 4, [Ph3GeGeMe2]2Ge(C6F5)2, containing electron donor (Me, Ph) and acceptor (C6F5) groups, by using a hydrogermolysis reaction in n-hexane. The molecular structures of 3 and 4 were studied by XRD. It was shown that, in its crystal form, 3 forms wide channels, in which the solvated nonpolar n-hexane molecule is present. The NMR (1 H, 13 C and 19 F), optical (UV/vis absorption, luminescence) and electrochemical (cyclic voltammetry) properties of both compounds were also studied. The impact of the substitution type (at the end of the compound, such as in 3, or within the compound, such as in 5, on the physical properties was also studied.
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