On the Chemistry of Zn−Zn Bonds, RZn−ZnR (R = [{(2,6-Prⁱ₂C₆H₃)N(Me)C}₂CH]): Synthesis, Structure, and Computations

Abstract

Potassium reduction of RZn(mu-I)2Li(OEt2)2 (R = [{(2,6-Pri2C6H3)N(Me)C}2CH]) affords the second compound with a Zn-Zn bond, RZn-ZnR. The air- and moisture-sensitive title compound was characterized by 1H NMR, elemental analyses, and single-crystal X-ray diffraction. The Zn-Zn bond was determined to be 2.3586(7) A; this value is only about 0.05 A longer than the Zn-Zn bond reported for Cp*Zn-ZnCp* (Cp* = C5Me5), the first reported compound with a Zn-Zn bond. In addition, density functional theory (DFT) computations on related model RZn-ZnR compounds provide insight into the intriguing Zn-Zn bond.

Solid-state and Solution Studies on a β-Diketiminate Zinc Hydride Complex

“…In 1a, the almost planar C(CN) 2 Zn six-membered rings adopt a co-planar orientation, whereas in 1b the rings are twisted by 42.6 • as was observed for [Mes nacnacZn(µ-H)] 2 [5]. As a consequence, the Zn-N bond lengths (1a: 1.971 (2) , which is elongated compared to that in the corre-sponding Zn-Zn bonded complexes Mesnacnac 2 Zn 2 (2.3813(8)Å) [11] and Dippnacnac 2 Zn 2 (2.3586(7)Å) [12]. In contrast, the unusual sodium hydride-bridged complex Ar Zn(µ-H)(µ-Na)ZnAr shows a significantly shorter Zn-Zn bond length (2.352(2)Å), which is essentially the same as observed for the Zn-Zn bonded complex Ar Zn-ZnAr (2.3591(9)Å) [6].…”

“…We became recently interested in β -diketiminate zinc halide complexes of the type MesnacnacZnX (Mesnacnac = [HC{C(Me)N(Mes)} 2 ], Mes = 2,4,6-Me 3 C 6 H 2 ; X = Cl, I) [8], which we believed to be suitable starting reagents for the synthesis of the corresponding low-valent complexes Zn 2 R 2 as well as the zinc hy-0932-0776 / 09 / 1100-1397 $ 06.00 c 2009 Verlag der Zeitschrift für Naturforschung, Tübingen · http://znaturforsch.com dride RZnH. Unfortunately, reactions with several reducing agents only resulted in the formation of ZnR 2 [9], whereas reduction of the comparable Dippsubstituted complex DippnacnacZnI (Dipp = 2,6-iPr 2 C 6 H 3 ) yielded Dippnacnac 2 Zn 2 [10].…”

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 .…”

Chemie von [Zn2Cp*2]: einwertiges {.ZnZnCp*}, stabilisiert in den metallreichen Verbindungen [(Pd,Pt)(GaCp*)a(ZnCp*)4−a(ZnZnCp*)4−a] (a=0, 2)

“…[9,10] Bisher ist nur wenig über die Chemie von [M 2 L 2 ] bekannt, [6][7][8] weshalb es auch nur wenige Publikationen über die Reaktivität des Zinkdimers gibt.…”

“…[4, 5,7] So sollte die Möglichkeit bestehen, [Zn 2 4 ] identifiziert werden konnten (siehe Hintergrundinformationen). [16] Die in Abbildung 1 dargestellte, durch eine EinkristallRöntgenstrukturanalyse erhaltene Molekülstruktur von 1 bestätigt die oktaedrische Anordnung der sechs Ga/Zn-Liganden um das zentrale Palladiumatom.…”