Chemie von [Zn₂Cp*₂]: einwertiges {^.ZnZnCp*}, stabilisiert in den metallreichen Verbindungen [(Pd,Pt)(GaCp*)_a(ZnCp*)_4−a(ZnZnCp*)_4−a] (a=0, 2)

Abstract

Unzertrennliches Zinkpärchen: Die Reaktion von homoleptischen {GaCp*}‐Verbindungen [M(GaCp*)4] (M=Pd, Pt; Cp*=Pentamethylcyclopentadienyl) mit [Zn2Cp*2] führt zur Bildung von [M(GaCp*)2(ZnCp*)2(ZnZnCp*)2] (siehe Bild; grau C, gelb Ga, grün Zn, blau Pd) und [M(ZnCp*)4(ZnZnCp*)4]. Beide Moleküle enthalten den neuartigen Liganden {ZnZnCp*} mit einer intakten Zn‐Zn‐Bindung.

Hume–Rothery Phase-Inspired Metal-Rich Molecules: Cluster Expansion of [Ni(ZnMe)6(ZnCp*)2] by Face Capping with Ni0(η6-toluene) and NiI(η5-Cp*)

“…8−12 In 2004, the first zinc(I) metallocene-like complex, [Zn 2 (η 5 -Cp*) 2 ], 13,14 containing the first stable Zn−Zn bond in a molecular complex was established. This compound turned out to be a good candidate for the facile generation of ZnZnCp* and ZnCp* one-electron donor ligands trapped at d 10 metals, to f o r m Z n -r i c h m o l e c u l e s o f t h e t y p e [ M -(ZnZnCp*) 4 (ZnCp*) 4 ] 15 (M = Ni, Pd, Pt) and [Pd-(ZnCp*) 4 (ZnMe) 2 {Zn(tmeda)}], 16 among others. 17 Interestingly, all of these compounds feature no significant structural changes if the Ga/Zn ratio is altered, as was found for the related intermetallic solid-state compounds.…”

“…In 2004, the first zinc(I) metallocene-like complex, [Zn 2 (η 5 -Cp*) 2 ], , containing the first stable Zn–Zn bond in a molecular complex was established. This compound turned out to be a good candidate for the facile generation of ZnZnCp* and ZnCp* one-electron donor ligands trapped at d 10 metals, to form Zn-rich molecules of the type [M(ZnZnCp*) 4 (ZnCp*) 4 ] (M = Ni, Pd, Pt) and [Pd(ZnCp*) 4 (ZnMe) 2 {Zn(tmeda)}], among others . Likewise, through selective Ga/Zn exchange reactions and involved redox processes, GaCp*-ligated transition-metal complexes [M(GaCp*) n ] can be transformed into all-Zn-ligated, pseudohomoleptic, and highly coordinated compounds [M(ZnR) 2 n ] , ( n ≥ 4; M = Mo, Ru, Rh, Ni, Pd, Pt; R = Me, Et, Cp*).…”

Stable ZnI‐Containing MOFs with Large [Zn70] Nanocages from Assembly of ZnII Ions and Aromatic [ZnI8] Clusters

“…As illustrated in FigureS2, Zn1 is coordinated by three nitrogen atoms (N1, N4, and N4A) from tetrazole rings (Zn1ÀN1 = 2.042(10) ,Z n1ÀN4 = 2.10 (2) )a nd three neighboring Zn1 atoms.T he distorted octahedron geometry aroundZ n2 is composed of four nitrogen atoms (N3, N3A, N3B, and N3C) from tetrazole rings and two oxygen atoms( O1 and O1A) from water molecules. The Zn2À N3 and Zn2ÀO1 bond lengths are 2.06(3) and2 .11(2) ,r espectively,a nd the O1-Zn2-N3 bond angles are 908.D ifferently from the coordination modes of Zn1 and Zn2, Zn3 atom is coordinated with four nitrogen atoms (N6, N6A, N6B, and N6C), forming an early ideal tetrahedron with the ZnÀNb ond length of 1.949(12) and the identical N-Zn3-N bond angle of 111.0(5)8.C omparedw ith 1,e ighte quivalent Zn1 atoms act as vertices to construct as lightly distorted cube with four Zn I ÀZn I bond lengths of 2.412 (5) and eight Zn I ÀZn I bond lengths of 2.394 (6) ,l eading to a[ Zn I 8 ]c ube with D 4h symmetry in 2.I t should be noted that all these Zn I ÀZn I bond lengths in 1 (2.443 )a nd 2 (2.394 and 2.412 )a re close to the sum of Pyykkç's single-bond covalentr adii (2.36 )a nd obviously shorter than the sum of Pauling's single-bond metallic radius 2.50 , [14,15] and are comparable with those reported in typical Zn 2 R 2 dimers from 2.295 to 2.418 , [16] for instance, Zn 2 (h 5 -C 5 Me 4 Et) 2 (2.295 ), [17] Zn 2 (h 5 -Cp*) 2 (Cp* = C 5 Me 5 ,2 .305 ), [18] [(dpp-bian)ZnZn(dpp-bian)] (dpp-bian = 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene, 2.332 ), [19] [Pd(GaCp*) 2 (ZnCp*) 2 -(ZnZnCp*) 2 ]( 2.345 ), [20] Ar'Zn(m-H)(m-Na)ZnAr" (Ar' = C 6 H 3 -2,6-(C 6 H 3 -2,6-iPr 2 ) 2 ,2 .352 ), [21] [{(iPr) 2 ATI} 2 Zn 2 ]( {(iPr) 2 ATI}H = N-isopropyl-2-(isopropylamino)troponimine, 2.353 ), [22] RZn-ZnR (R = [{(2,6-iPr 2 C 6 H 3 )N(Me)C} 2 CH],2 .359 ), [23] [Zn 2 (THF) 6 ][BAr 4 F] 2 (BAr 4 F = B{C 6 H 3 (CF 3 ) 2 } 4 ,2 .363 ), K 2 [(h 2 -Me 2 Si(NDipp) 2 )-ZnZn(h 2 -Me 2 Si(NDipp) 2 )] (Dipp = 2,6-iPr 2 C 6 H 3 ,2 .369 ), [24] [Na(THF) 2 ] 2 ·[LZn-ZnL] (L = [(2,6-iPr 2 C 6 H 3 )N(Me)C] 2 2À ,2 .399 ), [25] (Zn 2 (h 5 -Cp*) 2 (dmap) 2 (dmap = 4-dimethylaminopyridine, 2.418 ). [26] These results reveal the existence of ZnÀZn bonds between neighboring Zn atoms in 1 and 2.…”