Mrinal Bhunia, Christian Sandoval-Pauker, Dominik Fehn, Lauren Grant, Shuruthi Senthil, Michael Gau, Andrew Ozarowski, Jurek Krzystek, Joshua Telser, Balazs Pinter, Karsten Meyer, Daniel J Mindiola
The nitrido-ate complex [(PN)2Ti(N){μ2-K(OEt2)}]2 (1) reductively couples CO and isocyanides in the presence of DME or cryptand, to form rare, five-coordinate TiII complexes having a linear cumulene motif, [K(L)][(PN)2Ti(NCE)] (E = O, L = Kryptofix222, (2); E = NAd, L = 3 DME, (3); E = NtBu, L = 3 DME, (4); E = NAd, L = Kryptofix222, (5)). Oxidation of 2-5 with [Fc][OTf] afforded an isostructural TiIII center containing a neutral cumulene [(PN)2Ti(NCE)] (E = O, (6); E = NAd (7), NtBu (8)). Moreover, 1e- reduction of 6 and 7 in the presence of cryptand cleanly reformed corresponding discrete TiII complexes 2 and 5, which were further characterized by solution magnetization measurements and high- frequency and -field EPR (HFEPR) spectroscopy...
April 15, 2024: Angewandte Chemie