Lithium [Bis{benzoyl‐W(CO) 5 }(μ 2 ‐hydrogen)] − A Charge‐Assisted H + ‐Bridged Organometallic Complex Prepared by Selective Li + Ion Replacement

Efficient syntheses and isolation procedures of two closely related benzoyl−W(CO) 5 compounds, [{Li(diglyme)}{Ph(O)CW(CO) 5 }] ( 1 ) and [Li(diglyme) 2 ][(μ 2 ‐H){Ph(O)CW(CO) 5 } 2 ] ( 2 ) are reported. The empirical formulae of 1 and 2 differ only in that the latter contains half the number of Li + ions, with the balance of cations replaced by protons through an acidic silica gel filtration procedure. X‐ray structural investigations of both compounds revealed a self‐assembled polymeric Li + ‐bridged structure for 1 , and a strikingly dissimilar H + ‐bridged structure for 2 , thereby emphasising the important influences of strong, charge‐assisted hydrogen bonds on solid‐state structures. Possible implications of this novel route to charge‐assisted hydrogen bonds for crystal engineering are discussed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)