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Convenient synthetic routes to the compounds WBr 4 (1), WBr 4 (MeCN) 2 (2), WBr 4 (THF) 2 (3), WBr 4 (PPh 3 ) 2 (4), WBr 4 (bpy) (6), and WBr 4 (dppe) (7) are described via the solution-phase oxidation of W(CO) 6 using two equivalents of bromine. These one-pot syntheses use inexpensive and readily available starting materials and produce analytically pure compounds with high yields under mild conditions. Attempts to grow crystals of 1 by heating in a sealed tube at *200°C resulted in formation of the previously reported compound WOBr 4 . Attempts to recrystallize 4 from dichloromethane solution produced [HPPh 3 ] 2 [WBr 6 ] (5). X-ray crystallographic studies showed that 5 consists of an array of [WBr 6 ] 2-anions and [HPPh 3 ] ? cations and that 7ÁCH 2 Cl 2 has the expected sixcoordinate tungsten center. The synthesis of tungsten(IV) bromide compounds via oxidation of W(CO) 6 is simple and provides better yields than previously reported methods. This synthetic route also has many advantages over the syntheses of similar tungsten(IV) chloride compounds which involve reduction of WCl 6 .