Reaktion von Bis(methylzink)-1,2-dipyridyl-1,2-bis(tert-butyldimethylsilylamido)ethan mit Triisopropylsilylphosphan und -arsan

Abstract

Frau Professor Marianne Baudler zum 80. Geburtstag gewidmet Inhaltsu È bersicht. Die Umsetzung von Bis(methylzink)-1,2-dipyridyl-1,2-bis(tert-butyldimethylsilylamido)ethan (1) mit Triisopropylsilylphosphan fu È hrt in guten Ausbeuten zu dem dreikernigen Komplex [1,2-Dipyridyl-1,2-bis(tert-butyldimethylsilylamido)ethan]trizink-bis(l-triisopropylsilylphosphandiid) (2). Zwei der Zinkatome weisen die Koordinationszahl von vier auf, wa È hrend das dritte Metallzentrum zwischen den Phosphoratomen mit einem gewinkelten P±Zn±P-Fragment auftritt. Die Reaktion von 1 mit Triisopropylsilylarsan verla È uft analog, allerdings la È ût sich das entstandene [1,2-Dipyridyl-1,2-bis(tert-butyldimethylsilylamido)ethan]trizink-bis(l-triisopropylsilylarsandiid) (3) nicht analysenrein isolieren. Reaction of Bis(methylzinc)-1,2-dipyridyl-1,2-bis(tert-butyldimethylsilylamido)ethane with Triisopropylsilylphosphane and -arsaneAbstract. The reaction of bis(methylzinc)-1,2-dipyridyl-1,2-bis(tert-butyldimethylsilylamido)ethane (1) with triisopropylsilylphosphane gives the three-nuclear complex [1,2-dipyridyl-1,2-bis(tert-butyldimethylsilylamido)ethane]trizincbis(l-triisopropylsilylphosphanediide) (2). Two zinc atoms show the coordination number of four whereas the third metal center is located between the two phosphorus atoms with a bent P±Zn±P-moiety. The reaction of 1 with triisopropylsilylarsane proceeds analoguesly, however, we were not able to isolate analytically pure [1,2-dipyridyl-1,2-bis(tert-butyldimethylsilylamido)ethane]trizinc-bis(l-triisopropylsilylarsanediide) (3).

Synthesis and Characterization of Novel Oxo-Centered Phosphanylzincates of Potassium and Cesium with a Central Zn6O2P4 Double-Heterocubane Cage

“…Because of the small coordination number of 2 for Zn4, a very short average Zn4−P bond of 221.2 pm is observed. The deviation of the P3−Zn4−P4 angle of 163.38(8)° from linearity is a common feature for such structural fragments, and has been observed earlier. − …”

Mechanistic studies on the hydrolysis of a dimeric alkylzinc bis(2-pyridylmethyl)amide

“…Proteolysis with acetamide quantitatively yields 1,2-dipyridyl-1,2-bis(trialkylsilyl)ethane [10]. A primary phosphane is doubly deprotonated and, in this process, the amide ligand and the zincbound alkyl groups both react to form their corresponding alkanes and amines [11]. Hydrolysis with water leads to NSi bond cleavage under formation of siloxanes.…”

(EtZn)4Zn2(PSitBu3)4 – a Homometallic Phosphanediide of Zinc with a Novel Zn6P4 Cage

“…[5] or stabilized by a multidentate ligand [9]. Here we report the first example of a novel Zn n P m cage built only by zinc atoms and phosphanediide substituents.…”

“…The zincbonded phosphanediides prepared so far are shielded by bulky tris(trimethylsilyl)methyl groups [6] or embedded in a matrix of zinc(II) chloride with additional trialkylphosphane ligands [5] or stabilized by a multidentate ligand [9]. Here we report the first example of a novel Zn n P m cage built only by zinc atoms and phosphanediide substituents.…”

“…Comparable short Zn-P bonds were observed for [(Me 3 Si) 3 CZn]PSiiPr 3 (223.2 pm [6]) and for [1,2-dipyridyl-1,2-bis(tert-butyldimethylsilylamido)ethane]trizinc bis(triisopropylsilylphosphanediide) (224.2 pm [9]). The latter shows a P-Zn-P bond angle of 154.0…”