Controlled cluster expansion at a Zintl cluster surface

TY - JOUR

T1 - Controlled cluster expansion at a Zintl cluster surface

AU - Townrow, Oliver P.E.

AU - Weller, Andrew S.

AU - Goicoechea, Jose M.

N1 - Funding Information: We thank Shell Global Solutions International B.V., the University of Oxford and the EPSRC for financial support of this research (Industrial CASE studentship O.P.E.T.; EP/M024210 ASW). The University of Oxford is also acknowledged for access to Chemical Crystallography facilities. Publisher Copyright: © 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

PY - 2024/1/15

Y1 - 2024/1/15

N2 - Reaction of the tris-hypersilyl nonagermanide Zintl cluster salt, K[Ge9(Hyp)3] (Hyp=Si(SiMe3)3) with [Rh(η2,η2-L)Cl]2 (L=1,5-cyclooctadiene, COD; norbornadiene, NBD) afforded eleven- and twelve-vertex homo-multimetallic clusters by cluster core expansion. Using a stepwise procedure, starting from the Zintl cluster [Rh(COD){Ge9(Hyp)3}] and [Ir(COD)Cl]2, this methodology was expanded for the synthesis of eleven-vertex hetero-multimetallic clusters. A mechanism for the formation of these first examples of closo eleven-vertex Zintl clusters is proposed, informed by density functional theory calculations.

AB - Reaction of the tris-hypersilyl nonagermanide Zintl cluster salt, K[Ge9(Hyp)3] (Hyp=Si(SiMe3)3) with [Rh(η2,η2-L)Cl]2 (L=1,5-cyclooctadiene, COD; norbornadiene, NBD) afforded eleven- and twelve-vertex homo-multimetallic clusters by cluster core expansion. Using a stepwise procedure, starting from the Zintl cluster [Rh(COD){Ge9(Hyp)3}] and [Ir(COD)Cl]2, this methodology was expanded for the synthesis of eleven-vertex hetero-multimetallic clusters. A mechanism for the formation of these first examples of closo eleven-vertex Zintl clusters is proposed, informed by density functional theory calculations.

KW - Germanium

KW - Iridium

KW - Metal Alloys

KW - Rhodium

KW - Zintl Clusters

UR - http://www.scopus.com/inward/record.url?scp=85179686200&partnerID=8YFLogxK

U2 - 10.1002/anie.202316120

DO - 10.1002/anie.202316120

M3 - Article

C2 - 38010628

AN - SCOPUS:85179686200

SN - 1433-7851

VL - 63

JO - Angewandte Chemie International Edition

JF - Angewandte Chemie International Edition

IS - 3

M1 - e202316120

ER -