Diketiminate-Supported Manganese and Zinc Complexes

A two-step procedure is employed based on the literature procedure for LMe , Pr2MnI(THF), which first generates the potassium salt KLMe Pr2 prior to its reaction with MnL.1 The preparation of the potassium salt of the p-diketimine fl Me, Pr2 was reported by Mair and coworkers from HLMe, Pr2 and KN(SiMe3)2 in relatively low yield (27%).2 Winter and coworkers have reported a related THF adduct from KH.3 Here, the same reagents in diethyl ether give a base-free potassium salt that was used to introduce LMe Pr2 into manganese and zinc complexes. 

All reactions were performed using standard Schlenk and drybox techniques. All the solvents except dichloromethane (P4O10) were distilled from sodium under dry nitrogen. 12 M HC1, Mnl2, Znl2, and BuLi in hexane were purchased from Aldrich. 

Step 1 A suspension of KH (0.18 g, 4.5 mmol) and HLMe Pr2 (1.67 g, 4.00 mmol) in diethyl ether (50 mL) is stirred at room temperature for 3 days. After filtration, the light yellow filtrate is concentrated to ca. 10 mL and stored at 26°C for 24 h to afford crystalline solid. Yield 1.59 g (87%). 

Institut fur Anorganische Chemie, Universitat Gottingen, D-37077 Gottingen, Germany. f Department of Chemistry, Georgetown University, Washington, DC 20057-1227. 

ff r2]y[ni(THF) is soluble in THF and toluene and sparingly soluble in Et20 and ra-pentane. The bound THF ligand may be readily removed by refluxing in toluene (see below) and may be displaced by other Lewis bases such as a /V-heterocyclic carbene ligand.1 

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