Syntheses and structures of W2(µ-Cl)3Cl6– and W2(µ-Cl)2Cl82–, new d2–d2 confacial and edge-sharing bioctahedral ditungsten compounds, and a convenient synthesis of W2(µ-Cl)3Cl62–

Abstract

(NR₄)W₂Cl₉ and (NR₄)₂W₂Cl₁₀, prepared by addition of NR₄Cl (R = alkyl) to (WCl₄)_x powder in CH₂Cl₂, have confacial [WW, 2.689(1) Å] and edge-sharing bioctahedral [WW, 2.792(1) Å] structures, respectively, as NBnEt₃⁺ salts, and convert with added NR₄Cl to (NR₄)₂W₂Cl₉ and (NR₄)WCl₆ and eventually (NR₄)₂WCl₆; (NR₄)W₂Cl₉ can be converted to (NR₄)₂W₂Cl₁₀ by NR₄Cl at –30 °C.