Smooth reVersible olefin insertion of ethyl acrylate, acrylonitrile, ethylene, dimethyl fumarate, and dimethyl maleate into MHCp(CO) 3 (M ) Mo (1a), W (1b)) has been catalyzed by Pd(PPh 3 ) 4 (4) or Pd(ethyl acrylate)(dppe) (8) at room temperature.Transition metal-hydride addition to olefins (so-called olefin insertion) is one of the most well-established, important, fundamental reactions in organometallic catalysis. 1 Such a process is frequently facile and reversible, as observed in transition-metal-catalyzed olefin isomerization 2 as well as in disproportionation of the alkyl ligands in dialkylplatinum(II) complexes. 3 However, for some transition-metal hydrides such as the molybdenum and tungsten hydrides MHCp(CO) 3 (M ) Mo (1a), W (1b)), olefin insertion did not take place, though alkynes with a strong electron-withdrawing group can insert. 4 Insertion and its reverse, -hydrogen elimination processes, generally require a coplanar transition state or intermediate consisting of a metal hydride and a CdC double bond. 5 We recently reported enhanced -hydrogen elimination in a heterodinuclear ethylplatinum-molybdenum complex, (dppe)EtPtMoCp(CO) 3 (2), giving the corresponding hydridoplatinummolybdenum complex (dppe)HPt-MoCp(CO) 3 (3a), which further reacts with alkynes having an electron-withdrawing group to cause facile reductive elimination to give MoHCp-(CO) 3 and Pt(alkyne)(dppe). 6 When a terminal alkyne is employed, the succeeding Markovnikov addition of MoHCp-(CO) 3 to the coordinated alkyne takes place to give the new heterodinuclear µ-alkenyl complexes (dppe)(µ-CH 2 dCR)PtMoCp(µ-CO)(CO). These facts prompted us to investigate the
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