Substitution of Hyp (Hyp = Si(SiMe₃)₃) at metalloid [Ge₉(Hyp)₃]⁻ clusters using phosphine stabilized Au(i)Cl

Abstract

We present two new intermetalloid cluster compounds [(nBu3P)AuGe9(Hyp)2Au(PnBu3)]2 (1) and [Au(iPr2POC6H4OPiPr2)AuGe9(Hyp)2]2 (2) which are obtained from the reaction of KGe9(Hyp)3 (Hyp = Si(SiMe3)3) with respective Au(I) phosphine precursors. The products...

New Intermetalloid Ge9‐clusters with Copper and Gold: Filling Vacancies in the Cluster Chemistry of [Ge9(Hyp)3]− (Hyp=Si(SiMe3)3)

“…The clusters found and presented in this work as well as the theoretical calculations show that the clusters linked by a central metal atom are formed via singly coordinated clusters. Originally our group proposed the following reaction path for the formation of [Ge 9 (Hyp 3 )AuGe 9 (Hyp 6), Au3-Ge18 267.66(6), Au3-Ge19 266.01(6), Ge1-Ge2 280.39(9), Ge1-Ge3 283.29(9), Ge2-Ge3 279.78(9), Ge11-Ge12 276.54(10), Ge11-Ge13 277.95(9), Ge12-Ge13 275.56(9), Ge7-Ge8 289.17(8), Ge7-Ge9 293.02(8), Ge8-Ge9 288.68(8), Ge17-Ge18 290.21(8), Ge17-Ge19 293.23(9), Ge18-Ge19 295.41(8), Ge1-Ge9 326.05(9), Ge2-Ge8 338.29(9), Ge3-Ge7 330.67 (9), Ge11-Ge19 330.85(9), Ge12-Ge17 335.36(9), Ge13-Ge18 331.37(9), Au1-ctp1 197.62(4), Au3-ctp2 208.95(4), Au3-ctp3 206.54(4), P1-Au1-ctp1 177.428(61), ctp2-Au3-ctp3 177.661 (23). *ctp is the centre of gravity for the Ge atoms bonded to the coinage metal Scheme 1.…”

“…While the naked Zintl‐ions often show this η 4 ‐coordination it is less common for Ge 9 (Hyp) 3 moieties like within the ( i Pr NHC)CuGe 9 (Hyp) 3 cluster [22] . Another pair of cluster compounds where this difference between η 3 and η 4 coordination is observed is that of the dimeric [( n Bu 3 P)AuGe 9 (Hyp) 2 Au(P n Bu 3 )] 2 , [23] where both Au atoms are bonded η 3 to the Ge 9 cluster cores, while in case of [( i Pr 3 P)CuGe 9 (SiPh 3 ) 2 Cu(P i Pr 3 )] 2 [17] the Cu atoms that link both clusters are bonded η 3 to the Ge 9 cores and the terminal Cu atoms are bonded η 4 . This hints at a preferred η 4 coordination in the case of copper which can't be realized in 1 due to steric reasons.…”

“…C and Si atoms as stick model, H atoms omitted for clarity. Selected bond lengths [pm] and angles [°]: Au1-Ge1 253.66(7), Au1-Ge2 257.44(7), Au1-Ge3 256.10(7), Au1-P1 232.5(2), Au3-Ge7 269.53(6), Au3-Ge8 267.25(6), Au3-Ge9 266.80(6), Au3-Ge17 267.19(6), Au3-Ge18 267.66(6), Au3-Ge19 266.01(6), Ge1-Ge2 280.39(9), Ge1-Ge3 283.29(9), Ge2-Ge3 279.78(9), Ge11-Ge12 276.54(10), Ge11-Ge13 277.95(9), Ge12-Ge13 275.56(9), Ge7-Ge8 289.17(8), Ge7-Ge9 293.02(8), Ge8-Ge9 288.68(8), Ge17-Ge18 290.21(8), Ge17-Ge19 293.23(9), Ge18-Ge19 295.41(8), Ge1-Ge9 326.05(9), Ge2-Ge8 338.29(9), Ge3-Ge7 330.67(9), Ge11-Ge19 330.85(9), Ge12-Ge17 335.36(9), Ge13-Ge18 331.37(9), Au1-ctp1 197.62(4), Au3-ctp2 208.95(4), Au3-ctp3 206.54(4), P1-Au1-ctp1 177.428(61), ctp2-Au3-ctp3 177.661(23). *ctp is the centre of gravity for the Ge atoms bonded to the coinage metal…”