Nako, AEAENakoChen, WWChenWhite, AJPAJPWhiteCrimmin, MRMRCrimmin2015-09-172016-08-202015-08-20Organometallics, 2015, 34 (17), pp.4369-43751520-6041http://hdl.handle.net/10044/1/26271The scope of the catalytic dehydrocoupling of primary and secondary amines with phenylsilanes has been investigated using [Y{N(SiMe3)2}3] and a four-coordinate analogue bearing a cyclometalated phosphonium methylide ligand. Inclusion of the phosphorus-based ligand on yttrium results in increased substrate scope in comparison to the tris(amide) analogue. While reversible C–H bond activation of the cyclometalated ligand was observed in stoichiometric experiments, D-labeling experiments and DFT calculations suggest that reversible ligand activation is not involved in silazane formation under catalytic conditions. We suggest that the extended reaction scope with the four-coordinate yttrium phosphonium methylide complex relative to the three-coordinate yttrium (tris)amide complex is a result of differences in the ease of amine inhibition of catalysis.This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://dx.doi.org/10.1021/acs.organomet.5b00607Journal Articlehttps://www.dx.doi.org/10.1021/acs.organomet.5b006071520-6041