Aminotroponiminatozinc(I) Complexes: Syntheses and Spectroscopic Analyses

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

“…Compared with 1 , eight equivalent Zn1 atoms act as vertices to construct a slightly distorted cube with four Zn I −Zn I bond lengths of 2.412 (5) Å and eight Zn I −Zn I bond lengths of 2.394 (6) Å, leading to a [Zn I 8 ] cube with D 4 h symmetry in 2 . It should be noted that all these Zn I −Zn I bond lengths in 1 (2.443 Å) and 2 (2.394 Å and 2.412 Å) are close to the sum of Pyykkö’s single‐bond covalent radii (2.36 Å) and obviously shorter than the sum of Pauling's single‐bond metallic radius 2.50 Å, and are comparable with those reported in typical Zn 2 R 2 dimers from 2.295 to 2.418 Å, for instance, Zn 2 (η 5 ‐C 5 Me 4 Et) 2 (2.295 Å), Zn 2 (η 5 ‐Cp*) 2 (Cp*=C 5 Me 5 , 2.305 Å), [(dpp‐bian)ZnZn(dpp‐bian)] (dpp‐bian=1,2‐bis[(2,6‐diisopropylphenyl)imino]acenaphthene, 2.332 Å), [Pd(GaCp*) 2 (ZnCp*) 2 (ZnZnCp*) 2 ] (2.345 Å), Ar′Zn(μ‐H)(μ‐Na)ZnAr“ (Ar′=C 6 H 3 ‐2,6‐(C 6 H 3 ‐2,6‐ i Pr 2 ) 2 , 2.352 Å), [{( i Pr) 2 ATI} 2 Zn 2 ] ({( i Pr) 2 ATI}H= N ‐isopropyl‐2‐(isopropylamino)troponimine, 2.353 Å), RZn‐ZnR (R=[{(2,6‐ i Pr 2 C 6 H 3 )N(Me)C} 2 CH], 2.359 Å), [Zn 2 (THF) 6 ][BAr 4 F] 2 (BAr 4 F=B{C 6 H 3 (CF 3 ) 2 } 4 , 2.363 Å), K 2 [(η 2 ‐Me 2 Si(NDipp) 2 )ZnZn(η 2 ‐Me 2 Si(NDipp) 2 )] (Dipp=2,6‐ i Pr 2 C 6 H 3 , 2.369 Å), [Na(THF) 2 ] 2 ⋅[LZn‐ZnL] (L=[(2,6‐ i Pr 2 C 6 H 3 )N(Me)C] 2 2− , 2.399 Å), (Zn 2 (η 5 ‐Cp*) 2 (dmap) 2 (dmap=4‐dimethylaminopyridine, 2.418 Å) . These results reveal the existence of Zn−Zn bonds between neighboring Zn atoms in 1 and 2 .…”

“…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.…”

New Perspectives for Aminotroponiminates: Coordination Chemistry, Redox Behavior, Cooperativity, and Catalysis

“…Since the redox‐activity of ATI ligands under reducing conditions sets in at strongly negative potentials {typically below –2.5 V vs. Fe(C 5 H 5 ) 2 /[Fe(C 5 H 5 ) 2 ] + },, ATI ligands can still act as redox‐innocent ligands for the stabilization of low‐valent metal centers. This has been exemplified for complexes containing central atoms such as Ti III , Zn I , Ge II , or Sn II , , , . Notably, these Ge II and Sn II ATI complexes can engage in Ge II /Sn II –M interactions with coinage metal cations M = Cu + , Ag + , Au + …”

A multicentre-bonded [ZnI]8 cluster with cubic aromaticity

“…Among the various bonding types, metal-metal (M-M) bonding has been one of the most important themes in inorganic chemistry since Cotton et al 3 [11][12][13][14][15][16][17][18][19][20][21][22][23] . However, these studies focus on the [Zn I 2 ] 2 þ dimeric species that are not sufficiently stable in air 11 .…”