67047-44-3Relevant academic research and scientific papers
Perfluoromethyl element ligands. XLIII [1]: Novel synthetic routes to binuclear complexes of the type MM′(CO)8ER2X (M/M′ = Mn/Mn, Mn/Re, Re/Re; E = P, As; R = CF3, Me; X = Hal,)
Grobe,Beysel,Kopp
, p. 2523 - 2536 (2008/10/08)
Mn(CO)5I reacts with compounds of the type (CF3)2EAsMe2 (E = P, As) as with the symmetric E2(CF3)4 ligands in the first step with cleavage of the E-As bond to yield the products (CO)5MnE(CF3)2 and Me2AsI. Reaction of the mononuclear complexes with excess of Mn(CO)5I leads in good yields to the known dinuclear compounds (CO)4Mn[E(CF3)2,I]Mn(CO)4 and CO. Me2AsI, the second product of the EAs cleavage, attacks the starting compound Mn(CO)5I giving cis-Mn(CO)4I(AsMe2I) and CO. This result encouraged us to thoroughly investigate the preparation of cis-M(CO)4X(EMe2Y) complexes with most of the possible combinations of M = Mn, Re; E = P, As and X,Y = Cl, Br, I. An alternative route to these compounds was opened by the cleavage of the dinuclear manganese or rhenium halides M2(CO)8X2 with the halophosphanes or -arsanes Me2EY. This route was found to be especially advantageous for the preparation of the rheniumcarbonyl precursors, since milder conditions than for the CO-substitution in Re(CO)5X compounds are sufficient for the halogen-bridged dinuclear complexes. Cis-M(CO)4X(EMe2Y) complexes were used as precursors for the synthesis of novel homo- and heterodinuclear complexes of the type (CO)4M(EMe2,X)M′(CO)4 by reacting the EY function with transition metal carbonylates Kat[M′(CO)5] (Kat = Na, Bu4N, Ph4As). Thus the preparation of a wide range of complexes was possible, which before had been successfully prepared by the direct reaction of Mn2(CO)10 with Me2EX only in few cases, e. g. with Me2AsI. Spectroscopic investigations, using the CO valence frequencies and the 1H-NMR data of the ligands EMe2Y or of the Me2E bridges, were applied to study the influence of the variables M, M′, E, X, Y and Kat on the reactivity of the mononuclear complexes and the bonding situation in both the mono- and the dinuclear systems. The new compounds were characterized by spectroscopic (IR, NMR, MS) and analytic methods (C, H).
