Reaction of transition-metal carbonylate anions and 1,1,1-tris(halogenomethyl)ethane. X-Ray crystal structures of tricarbonyl(η5-cyclopentadienyl)(1-methylcyclopropylmethyl)tungsten(II), and tetraethylammonium enneacarbonyliododirhenate(0)
Abstract
The interactions of 1, 1, 1-tris(halogenomethyl)ethanes, MeC(CH2X)3(X = Br or I) with the carbonyl anions [Fe(η5-C5H5)(CO)2]–, [M(η5-C5H5)(CO)3]–(M = Mo or W), [Ni(η5-C5H5)(CO)]–, [Mn(CO)5]–, and [Re(CO)5]– have been studied. All of the anions except [Mn(CO)5]– react to give 1-methylcyclopropylmethyl (C5H9) derivatives; [Mn(CO)5]– gives the acyl, Mn(CO)5(COC5H9). The structure of W(η5-C5H5)(CO)3(C5H9) has been determined by X-ray diffraction; the other species are characterised spectroscopically. From the reactions other products have been characterised; in particular [ Re(CO)5]– gives the previously unknown anion [ Re2I(CO)9]– whose structure in its [NEt4]+ salt has been determined by X-ray diffraction. The mechanisms of the various reactions involved are discussed.