Three different ways for the synthesis of the metalloid cluster [Ge₉(Hyp^tBuPh2)₃]⁻

Abstract

Dedicated to Professor Cameron Jones on the occasion of his 60th birthday.The metalloid cluster [Ge 9 (Hyp tBuPh2 ) 3 ]K (1) (Hyp tBuPh2 =Si-(SiMe 3 ) 2 (SitBuPh 2 )) is obtained through three different reaction courses. These are the disproportionation reaction of Ge I Br and subsequent substitution of the bromine atoms, the reaction of the germanium subhalide cluster Ge 14 Br 8 (PEt 3 ) 4 with KHyp tBuPh2 and the reaction of the Zintl phase K 4 Ge 9 with ClHyp tBuPh2 . The different reaction courses are described, together with the characterization and follow-up reaction of the new metalloid cluster 1.

A Series of Cyclopentadienyl Lanthanum Complexes with Metalloid Germanium Clusters

“…269 pm) is observed. The La−Ge bond lengths of 327.64 (7), 327.05 (8), and 323.73 (8) pm thereby show a more symmetric η 3 -coordination mode in 2 with respect to 1. Recently, a very similar dimeric structure with the same η 1 -and η 3 -coordination patterns of Ge 9 (Hyp) 2 clusters was found in the copper complexes by Fassler et al 24a and in the gold complexes by our group.…”

“…subhalide cluster Ge 14 Br 8 (PEt 3 ) 4 7 with KHyp t BuPh 2 affords the corresponding metalloid cluster. 8 Recently, a series of new boranyl-9 and phosphine-functionalized 10 Ge 9 clusters also deserve attention.…”

“…Along with the classical silylation method of K 4 Ge 9 with ClHyp t BuPh 2 [Hyp t BuPh 2 = Si(SiMe 3 ) 2 (Si t BuPh 2 )], which is successfully used for the synthesis of K[Ge 9 (Hyp) 3 ] and K 2 [Ge 9 (Hyp) 2 ], the disproportionation of a metastable Ge(I)Cl solution in the presence of KHyp t BuPh 2 , similar to the first discovery of the metalloid germanium cluster [Ge 9 (Hyp) 3 ] − , gives K[Ge 9 (Hyp t BuPh 2 ) 3 ]. Also, the reaction of the germanium subhalide cluster Ge 14 Br 8 (PEt 3 ) 4 with KHyp t BuPh 2 affords the corresponding metalloid cluster . Recently, a series of new boranyl- and phosphine-functionalized Ge 9 clusters also deserve attention.…”

“…Selected distances (pm) for 1: La1−Ge6 346.12(5), La1−Ge9 313.53(5), La1−Ge7′ 327.06(5), La1−Ge8′ 317.14(5), La1−Ge9′ 336.18(5). Selected distances (pm) for 2: La1− Ge4 327.64(7), La1−Ge7 327.05(8), La1−Ge8 323.73(8), La1−Ge9′ 312.14(8).…”