Divalent Titanium via Reductive N−C Coupling of a TiIV Nitrido with π‐Acids

The nitrido‐ate complex [(PN)2Ti(N){μ2‐K(OEt2)}]2 (1) (PN−=(N‐(2‐PiPr2‐4‐methylphenyl)‐2,4,6‐Me3C6H2) reductively couples CO and isocyanides in the presence of DME or cryptand (Kryptofix222), 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)) and characterization by CW X‐band EPR spectroscopy, revealed unpaired electron to be metal centric. Moreover, 1e− reduction of 6 and 7 in the presence of Kryptofix222cleanly reformed corresponding discrete TiII complexes 2 and 5, which were further characterized by solution magnetization measurements and high‐frequency and ‐field EPR (HFEPR) spectroscopy. Furthermore, oxidation of 7 with [Fc*][B(C6F5)4] resulted in a ligand disproportionated TiIV complex having transoid carbodiimides, [(PN)2Ti(NCNAd)2] (9). Comparison of spectroscopic, structural, and computational data for the divalent, trivalent, and tetravalent systems, including their 15N enriched isotopomers demonstrate these cumulenes to decrease in order of backbonding as TiII→TiIII→TiIV and increasing order of π‐donation as TiII→TiIII→TiIV, thus displaying more covalency in TiIII species. Lastly, we show a synthetic cycle whereby complex 1 can deliver an N‐atom to CO and CNAd. A titanium nitride undergoes N−C bond coupling with carbon monoxide and isocyanides to form TiII cumulene complexes [(PN)2Ti(NCE)]− (E=O, NAd, NtBu). Oxidation of these affords the TiIII cumulene [(PN)2Ti(NCE)]. Further oxidation affords a TiIV bis‐cumulene trans‐[(PN)2Ti(NCNAd)2]. Structural, electrochemical, and spectroscopic studies (HFEPR, CW X‐band, NMR and IR spectroscopies), including 15N isotopic labelling studies are presented and discussed to understand the bonding and topology.