Synthesis and reactivity of germyl complexes of manganese and rhenium

Intermolecular interactions in group 14 hydrides: Beyond CH···HC contacts

“…A similar analysis of the GeH···HGe contacts discloses a group of structures (fibpub, kajzok, GeD 4 , pallev, larpid, qelyip, papzai) with Ge···Ge distances shorter than the van der Waals radii sum (4.58 Å) that may or may not show simultaneous short Ge···H (< 3.49 Å) contacts, but all of them have H···H contacts longer than 2.7 Å. In most cases the interaction topology is of type 2 involving GeH 3 or GeH 2 groups, while in one case (fibpub) a 3:3 staggered conformation 4 , in another case the 1 type interaction (qelyip), and in yet another case a colinear 3 interaction (papzai) is found.…”

“…In most cases the interaction topology is of type 2 involving GeH 3 or GeH 2 groups, while in one case (fibpub) a 3:3 staggered conformation 4 , in another case the 1 type interaction (qelyip), and in yet another case a colinear 3 interaction (papzai) is found. The shortest Ge···Ge distance is 3.734 (fibpub) and the shortest Ge···H contacts appear at ∼3.34 Å (pallev, kajzok). The two shortest GeH····HGe contacts appear in two different crystal structures at 2.76 and 2.70 Å .…”

“…For silicon, an angular dependence of the R 3 SiAHÁÁÁHASiR 3 contact distances is seen in the CSD (Figure 1), whereby the closer the two interacting silyl groups are to being colinear (measured by the average SiAHÁÁÁSi angle), the shorter the HÁÁÁH distance can be, with several nearly collinear contacts being at distances shorter than 2.8 Å. [41,[57][58][59][60][61] A similar analysis of the GeAHÁÁÁHAGe contacts discloses a group of structures (fibpub, [62] kajzok, [63] GeD 4 , [64] pallev, [65] larpid, [66] qelyip, [67] papzai [68] ) with GeÁÁÁGe distances shorter than the van der Waals radii sum (4.58 Å) that may or may not show simultaneous short GeÁÁÁH (< 3.49 Å) contacts, but all of them have HÁÁÁH contacts longer than 2.7 Å. In most cases the interaction topology is of type 2 involving GeH 3 or GeH 2 groups, while in one case (fibpub) [62] a 3:3 staggered conformation 4, in another case the 1 type interaction (qelyip), [67] and in yet another case a colinear 3 interaction (papzai) [68] is found.…”

“…The two shortest GeAHÁÁÁÁHAGe contacts appear in two different crystal structures at 2.76 and 2.70 Å. [63,69] There are a few more examples with GeAHÁÁÁHAGe contacts between 2.8 and 2.9 Å, although they appear combined with GeAHÁÁÁHAC, [70] CAHÁÁÁHAC, [65] or CAHÁÁÁp [66,68] interactions at shorter distances.…”

Ruthenium and Osmium Germyl Complexes Derived from the Reactions of MXCl(PPh3)3 (M = Ru, Os; X = Cl, H) with Terphenylchlorogermylene (C6H3‐2,6‐Trip2)GeCl (Trip = 2,4,6‐iPr3C6H2)

“…Closely related to germylene and germylyne complexes are transition‐metal germyl complexes, which have been known for a long time and have continuously received considerable attention over the last several decades, mainly because of their relevance to the catalytic transformations involving germanium, and materials chemistry. [12a], The most versatile methods for the synthesis of transition‐metal germyl complexes involve either oxidative addition of the Ge–X bond GeXR 3 (X = H, Cl)[12a], or insertion of dihalogen species GeX 2 into the M–X bond[12a], [13a], , to give triorgano M‐GeR 3 or trihalogen M‐GeX 3 germyl derivatives. However, despite of the large number of germyl complexes of transition metals that have been prepared in recent years, ruthenium germyl complexes are still much less common,[13a], [15c], , , while the osmium congeners are even more limited , , , …”