American Chemical Society
om8b00379_si_001.pdf (7.01 MB)

[(dmpe)2MnH(C2H4)] as a Source of a Low-Coordinate Ethyl Manganese(I) Species: Reactions with Primary Silanes, H2, and Isonitriles

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journal contribution
posted on 2018-09-06, 19:15 authored by Jeffrey S. Price, David J. H. Emslie, Ignacio Vargas-Baca, James F. Britten
Wilkinson’s manganese­(I) ethylene hydride complex trans-[(dmpe)2MnH­(C2H4)] (1) reacts as a source of a low-coordinate manganese­(I) ethyl complex. This is illustrated in the reactivity of 1 toward a variety of reagents. Reactions of 1 with primary silanes RSiH3 (R = Ph, nBu) at 60 °C afforded ethane and the disilyl hydride manganese complexes [(dmpe)2MnH­(SiH2R)2] (4a, R = Ph; 4b, R = nBu). Additionally, reaction with H2 at 60 °C afforded ethane and the dihydrogen hydride complex [(dmpe)2MnH­(H2)] (5), which has previously been prepared by an alternate route. The proposed low-coordinate intermediate, [(dmpe)2MnEt], was not observed spectroscopically but could be trapped using isonitrile ligands; reaction of 1 with CNR (R = tBu, o-xylyl) afforded the manganese­(I) ethyl complexes [(dmpe)2MnEt­(CNR)] (6a, R = tBu; 6b, R = o-xylyl). Ethyl complex 6a did not react further with CNtBu at 80 °C. In contrast, complex 6b reacted with excess o-xylyl isonitrile to form 1,1-insertion products, including the iminoacyl complex [(dmpe)­Mn­(CNXyl)3{C­(NXyl)­CEt­(NXyl)}] (7, Xyl = o-xylyl). Complexes 4a, 6a,b, and 7, as well as the previously reported 1 and 5, have been crystallographically characterized, and DFT calculations have been employed to probe the accessibility of cis ethylene hydride and ethyl isomers of 1.


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