Abstract
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.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.