RGe(I)Ge(I)R Compound (R = PhC(NtBu)₂) with a Ge−Ge Single Bond and a Comparison with the Gauche Conformation of Hydrazine

Abstract

This article reports the reduction of the chloride [PhC(NtBu) 2 ]GeCl with potassium in THF to afford the reddish crystals of [PhC(NtBu) 2 ] 2 Ge 2 (2). The molecule of 2 contains a Ge-Ge bond. The X-ray structure and DFT calculation indicate that the Ge-Ge bond possesses an unusual gauche-bent geometry. The Ge-Ge bond length in 2 is 2.570 Å, which is very close to the single Ge-Ge interaction (2.61 Å) but significantly longer than that for typical digermenes, R 2 GeGeR 2 (2.21-2.51 Å) and the two structurally characterized digermynes (2.2850 Å and 2.2060 Å), which proves that there is no multiple bond character in 2.

Iron Complexes with Stabilized Germylenes: Syntheses and Characterizations

“…The three-coordinate germanium atom adopts a pyramidal geometry, as generally observed for analogues to monomeric amidinato-chlorogermylenes. 4,13,15 The treatment of 1 with Fe 2 (CO) 9 overnight in THF at room temperature afforded the corresponding iron complexes 3 after elimination of Fe(CO) 5 in relatively good yields (78% for 3a and 92% for 3b) (Scheme 2).…”

“…1 H NMR (300.18 MHz, C 6 D 6 ): δ 1.07 (s, 9H, CMe 3 ); 1.21 (d, 3 J HH = 6.3 Hz, 6H, CHMe 2 ); 1.27 (d, 3 J HH = 6.3 Hz, 6H, CHMe 2 ); 1.30 (d, 3 J HH = 6.3 Hz, 6H, CHMe 2 ); 1.35−1.52 (large signal, 6H, CHMe 2 ); 1.56 (s, 9H, CMe 3 ); 3.92 (sept., 3 J HH = 6.6 Hz, 1H, CHMe 2 ); 4.07 (sept., 3 J HH = 6.3 Hz, 2H, CHMe 2 ); 4.32 (sept., 3 J HH = 6,3 Hz, 1H, CHMe 2 ). 13 Reaction of 1a,b with Fe 2 (CO) 9 . A solution of 1a (0.24 g, 0.68 mmol) in THF (4 mL) was added to a suspension of Fe 2 (CO) 9 (0.20 g, 0.68 mmol) in THF (4 mL) at −40°C.…”

A Remarkable Base‐Stabilized Bis(silylene) with a Silicon(I)–Silicon(I) Bond

“…[15] Compound 2 possesses a gauche-bent conformation. This structural feature of 2 is akin to that of the Ge I dimer, [11] which also favors a gauche-bent geometry, as do the isolobal equivalents hydrazine and diphosphine. [16] It is interesting to mention that a bis(carbene) with a C I À C I bond has not been reported to date.…”

“…We were recently successful in using an amidinate ligand with tBu substituents on the nitrogen atoms to stabilize heteroleptic silylenes and a Ge I dimer. [10,11] It seems that such a ligand might also stabilize a Si I compound with a Si I À Si I single bond. Our preliminary results in this direction are reported herein.…”

A Remarkable Base‐Stabilized Bis(silylene) with a Silicon(I)–Silicon(I) Bond

“…[9] To our knowledge, only one compound consisting of a Si À Si single bond and a lone pair of electrons on each Si atom was reported to date. [10,11] It seems that such a ligand might also stabilize a Si I compound with a Si I À Si I single bond. This situation is unique, because each Si center which features a lone pair of electrons is simultaneously involved in bonding.…”