Synthesis and Reactivity of Multiple Phosphine-Functionalized Nonagermanide Clusters

Felix S. Geitner; Wilhelm Klein; Thomas F. Fässler

doi:10.1002/anie.201803476

Synthesis and Reactivity of Multiple Phosphine-Functionalized Nonagermanide Clusters

Felix S. Geitner, Wilhelm Klein, Thomas F. Fässler

Chair of Inorganic Chemistry with Focus on New Materials

Research output: Contribution to journal › Article › peer-review

33 Scopus citations

Abstract

Herein we report on the synthesis of the first multiple phosphine-substituted nonagermanide clusters in a one-step reaction from K₄Ge₉. Their reactions towards various transition metal complexes show a large variety of reactive sites. The novel threefold phosphine-functionalized [Ge₉] clusters [Ge₉{PRR^I}₃]⁻ {R: NⁱPr₂; R^I: NⁱPr₂ (1 a) or ^tBu (2 a)} are obtained by reaction of pristine [Ge₉]⁴⁻ clusters with the respective chlorophosphines. Subsequent reactions with NHC^DippCuCl yield neutral compounds (NHC^DippCu)[Ge₉{P(NⁱPr₂)₂}₃] (3) and (NHC^DippCu)[Ge₉{P(NⁱPr₂)^tBu}₃] (4), respectively. The reaction of neutral compound 3 with Cr(CO)₅(thf) yields the first uncharged fivefold substituted [Ge₉] cluster (NHC^DippCu)₂[Ge₉{P(NⁱPr₂)₂}₂Cr(CO)₅] (5) via a ligand exchange reaction at the [Ge₉] cluster core. Compounds 3 and 5 are characterized by single crystal structure determination.

Original language	English
Pages (from-to)	14509-14513
Number of pages	5
Journal	Angewandte Chemie International Edition in English
Volume	57
Issue number	44
DOIs	https://doi.org/10.1002/anie.201803476
State	Published - 26 Oct 2018

Keywords

cage molecules
cluster
germanium
phosphorus
reactivity

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title = "Synthesis and Reactivity of Multiple Phosphine-Functionalized Nonagermanide Clusters",

abstract = "Herein we report on the synthesis of the first multiple phosphine-substituted nonagermanide clusters in a one-step reaction from K4Ge9. Their reactions towards various transition metal complexes show a large variety of reactive sites. The novel threefold phosphine-functionalized [Ge9] clusters [Ge9{PRRI}3]− {R: NiPr2; RI: NiPr2 (1 a) or tBu (2 a)} are obtained by reaction of pristine [Ge9]4− clusters with the respective chlorophosphines. Subsequent reactions with NHCDippCuCl yield neutral compounds (NHCDippCu)[Ge9{P(NiPr2)2}3] (3) and (NHCDippCu)[Ge9{P(NiPr2)tBu}3] (4), respectively. The reaction of neutral compound 3 with Cr(CO)5(thf) yields the first uncharged fivefold substituted [Ge9] cluster (NHCDippCu)2[Ge9{P(NiPr2)2}2Cr(CO)5] (5) via a ligand exchange reaction at the [Ge9] cluster core. Compounds 3 and 5 are characterized by single crystal structure determination.",

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author = "Geitner, {Felix S.} and Wilhelm Klein and F{\"a}ssler, {Thomas F.}",

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year = "2018",

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AU - Klein, Wilhelm

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Y1 - 2018/10/26

N2 - Herein we report on the synthesis of the first multiple phosphine-substituted nonagermanide clusters in a one-step reaction from K4Ge9. Their reactions towards various transition metal complexes show a large variety of reactive sites. The novel threefold phosphine-functionalized [Ge9] clusters [Ge9{PRRI}3]− {R: NiPr2; RI: NiPr2 (1 a) or tBu (2 a)} are obtained by reaction of pristine [Ge9]4− clusters with the respective chlorophosphines. Subsequent reactions with NHCDippCuCl yield neutral compounds (NHCDippCu)[Ge9{P(NiPr2)2}3] (3) and (NHCDippCu)[Ge9{P(NiPr2)tBu}3] (4), respectively. The reaction of neutral compound 3 with Cr(CO)5(thf) yields the first uncharged fivefold substituted [Ge9] cluster (NHCDippCu)2[Ge9{P(NiPr2)2}2Cr(CO)5] (5) via a ligand exchange reaction at the [Ge9] cluster core. Compounds 3 and 5 are characterized by single crystal structure determination.

AB - Herein we report on the synthesis of the first multiple phosphine-substituted nonagermanide clusters in a one-step reaction from K4Ge9. Their reactions towards various transition metal complexes show a large variety of reactive sites. The novel threefold phosphine-functionalized [Ge9] clusters [Ge9{PRRI}3]− {R: NiPr2; RI: NiPr2 (1 a) or tBu (2 a)} are obtained by reaction of pristine [Ge9]4− clusters with the respective chlorophosphines. Subsequent reactions with NHCDippCuCl yield neutral compounds (NHCDippCu)[Ge9{P(NiPr2)2}3] (3) and (NHCDippCu)[Ge9{P(NiPr2)tBu}3] (4), respectively. The reaction of neutral compound 3 with Cr(CO)5(thf) yields the first uncharged fivefold substituted [Ge9] cluster (NHCDippCu)2[Ge9{P(NiPr2)2}2Cr(CO)5] (5) via a ligand exchange reaction at the [Ge9] cluster core. Compounds 3 and 5 are characterized by single crystal structure determination.

KW - cage molecules

KW - cluster

KW - germanium

KW - phosphorus

KW - reactivity

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Synthesis and Reactivity of Multiple Phosphine-Functionalized Nonagermanide Clusters

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