Recent developments in Zintl cluster chemistry

Abstract

Zintl anions have been known for more than a century and were studied systematically by Eduard Zintl in the 1930s. Since then, they have been investigated for their interesting structures, bonding, and physical properties - in solid Zintl phases, in solvate salts, and in solution. While their popularity remained limited for several decades, Zintl ion chemistry has recently experienced a renaissance as a result of breakthroughs regarding their modifications into multinary anions that include transition metal atoms, their organic derivatization, and their oxidative linkage. A plethora of reports from the past two decades - demonstrating the ever growing variety of Zintl ion chemistry - have been since summarized in several review articles. Herein, we intend to present the most recent developments, which also shed light on Zintl anions and clusters as useful precursors for materials development, as illustrated by one recent example.

Expansion of Magnetic Aromaticity Criteria to Multilayer Structures: Magnetic Response and Spherical Aromaticity of Matryoshka‐Like Cluster [Sn@Cu12@Sn20]12−

“…Main group clusters have rich structural diversity offering aesthetically pleasing architectures alongside intriguing bonding patterns and related properties . In recent years, research on Zintl clusters has been encouraged by their potential to form versatile novel derivatives, such as organo‐Zintl, organometallic‐Zintl, and heterometallic species .…”

“…Main group clustersh ave rich structurald iversity offering aestheticallyp leasing architectures alongside intriguing bonding patterns and relatedp roperties. [1][2][3][4][5][6] In recent years, research on Zintl clusters has been encouraged by their potentialt oform versatile novel derivatives, [2,7,8] such as organo-Zintl, [9][10][11][12] organometallic-Zintl, [13,14] and heterometallic species. [15][16][17] Moreover, among all-metal species, Zintl clusters are promising candidates to host aromaticity,w hich provides their remarkable stability.…”

A Neutral Heteroatomic Zintl Cluster for the Catalytic Hydrogenation of Cyclic Alkenes

“…To the best of our knowledge, this is the first instance of the use of Zintl clusters in homogeneous catalysis. 13 , 14 …”

Samarium Polyarsenides Derived from Nanoscale Arsenic

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Zintl phases of arsenic and molecular compounds containing Zintl-type polyarsenide ions are of fundamental interest in basic and applied sciences.U nfortunately,t he most obvious and reactive arsenic source for the preparation of defined molecular polyarsenide compounds,y ellowa rsenic As 4 ,i sv ery inconvenient to prepare and neither storable in pure form nor easy to handle.Herein, we present the synthesis and reactivity of elemental As 0 nanoparticles (As 0 Nano ,d= 7.2 AE 1.8 nm), which were successfully utilized as ar eactive arsenic source in reductive f-element chemistry.S tarting from [Cp* 2 Sm] (Cp* = h 5 -C 5 Me 5 ), the samarium polyarsenide complexes [(Cp* 2 Sm) 2 (m-h 2 :h 2 -As 2 )] and [(Cp* 2 Sm) 4 As 8 ]w ere obtained from As 0 nano ,therebygenerating the largest molecular polyarsenide of the f-elements and circumventing the use of As 4 in preparative chemistry.Zintl phases and Zintl ions have been thoroughly investigated in the solid state and molecular chemistry for decades. [1] Particularly,p olypnictides (Pn = P, As,S b, Bi) feature arich chain and cage chemistry with, for example,the polycyclic [P 7 ] 3À anion as one of the most prominent examples. [2] When it comes to molecular coordination compounds,w hich incorporate polypnictide ions,p revious research has been almost entirely focused on transition metals and phosphorus.

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“…Zintl phases and Zintl ions have been thoroughly investigated in the solid state and molecular chemistry for decades. [1] Particularly,p olypnictides (Pn = P, As,S b, Bi) feature arich chain and cage chemistry with, for example,the polycyclic [P 7 ] 3À anion as one of the most prominent examples. [2] When it comes to molecular coordination compounds,w hich incorporate polypnictide ions,p revious research has been almost entirely focused on transition metals and phosphorus.…”