DIHYDRIDE FORMATION VERSUS H2-ELIMINATION IN THE PROTONATION OF THE HETEROBIMETALLIC FEPT COMPLEX (CO)3FE(MU-H)(MU-PCY2)PT(PET3)2

The reaction of Li[Fe(CO)4(PCy2)] with rrans-PtCl(H)(PEt3)2 results in the formation of the hydride complex (CO)3Fe(μ-H)((x-PCy2)Pt(PEt3)2, 1. This heterobimetallic, phosphido-bridged complex reacts with one equivalent of HBF4Et20 to give the complex [(CO)3Fe(μ H)2(μ-PCy2)Pt(PEt3)2][BF4], 2, which contains two bridging hydride ligands. This species is isolated and fully characterized by 31P{1H} and 1H NMR and infrared spectroscopy. In contrast, 1 reacts with one equivalent of HC1 · DMA (DMA = dimethylacetamide) to give the complex (CO)3CIFe(μ-PCy2)Pt(PEt3)2, 3. This species is the result of oxidative addition of HC1 with subsequent reductive elimination of H2(g). This complex is fully characterized by 31P{1H} and 1H NMR, infrared spectroscopy and an X-ray crystal structure determination. 3 crystallizes in the space group PI with a = 10.037(4) Å, b= 10.644(3) Å, c= 17.137(9) A, α = 102.80(3)°, β = 76.74(3)°,-γ = 103.99(3)°, V = 1702(1) Å3,and Z = 2. The structure was refined to R = 2.54% and Rw = 2.73% for 4056 reflections with F0 2 > 3a(F0 2). © 1990 E-flow National Research Council of Canada. All Rights Reserved.