114674-85-0Relevant academic research and scientific papers
Vinylidene Transition-Metal Complexes, VI The Rhodium Compounds C5H5Rh(=C=CHR)PiPr3 as Building Blocks for the Synthesis of Heterometallic Di- and Trinuclear Vinylidene-Bridged Complexes
Werner, Helmut,Alonso, Francesco Javier Garcia,Otto, Heiko,Peters, Karl,Schnering, Hans Georg von
, p. 1565 - 1574 (2007/10/02)
The vinylidene rhodium complex C5H5Rh(=C=CH2)PiPr3 (1) reacts with C6H6Cr(CO)3 upon UV irradiation and with C5H5Mn(CO)2THF at room temperature to give the heterometallic dinuclear compounds (4) and (6), respectively.Treatment of 6 with HBF4 in ether leads, after metathetical exchange of the anion with NH4PF6, to the PF6 salt of the μ-ethylidyne cation (+) (7).The reactions of 1 and C5H5Rh(=C=CHR)PiPr3 (2: R = Me; 3: R = Ph) with Fe2(CO)9 give the dinuclear complexes (11-13) as the main products.In addition, small amounts of the trinuclear clusters 3-η1,η2-C=CHR)(μ-CO)2Fe2Rh(CO)4(PiPr3)C5H5> (14-16) are formed.The protonation of 11-13 with HBF4 gives the ionic compounds BF4 (17-19).The crystal and molecular structures of 6, 11, and 14 have been determined.The two dinuclear complexes 6 and 11 contain unsymmetrical bridging ligands (CO and C=CH2) probably as a consequence of the different electronic configuration of the metal atoms.The core of the trinuclear cluster 14 consists of an open Rh-Fe-Fe triangle which is triply bridged by the C=CH2 unit.
