Silyl-, Germyl-, and Stannyl-Pentacarbonylmetalates Of Chromium, Molybdenum, and Tungsten

Abstract
The new anions [R3M′M(CO)5] (R3M′ = Ph3Si, MePh2Si, Ph3Ge, Ph3Sn, Me3Sn, and Ph3Pb; M = Cr, Mo, W) have been prepared as tetraethylammonium salts by reaction of R3M′Li with [Et4N(ClM(CO)5]. The redistribution reaction between [Ph3SnW(CO)5] and [Cl3SnW(CO)5] affords [PhCl2SnW(CO)5] or [Ph2ClSnW(CO)5]. Anhydrous HCl reacts with [Ph3SiW(CO)5] and [Ph3GeW(CO)5] to form [ClW(CO)5] but with [Ph3SnW(CO)5]to form [Cl3SnW(CO)5]. An insertion reaction of SnBr2 with [BrW(CO)5] forms the new anion [Br3SnW(CO)5] while SnCl2 and GeCl2 (from HGeCl3) react with [ClM(CO)5] to produce the known species [Cl3M'M(CO)5] (M′ = Ge, Sn; M = Cr, Mo, W). Infrared spectra in the carbonyl stretching region are reported for all anions.

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