Deuterated solvents were obtained from Cambridge Isotope Laboratories and were degassed, dried, and distilled prior to use.

Solvents were dried by distillation from sodium wire/benzophenone. General InformationĪll manipulations were performed with rigorous exclusion of oxygen and moisture in Schlenk-type glassware on a dual manifold Schlenk line or in N 2 filled glove box (mBraun 120-G) with a high-capacity recirculator (<0.1 ppm O 2). Here, we describe our attempt to isolate Ti I species using the steric bulk and the mono-anionic nature of the guanidinate ligands, and report the synthesis and structures of Ti IV guanidinate and its reduction to Ti III instead of Ti I complex. In comparison to Ti II, isolation of Ti I species is a challenge to chemists. The chemistry of Ti II complexes is mainly dominated by cyclopentadiene (Cp) ligands, however, N-containing ligands (aminopyridine) have also been successfully applied for Cp-free Ti II species. Divalent titanium has already been widely used for a variety of metal-promoted organic transformations, which shows that Ti I species might be very interesting in terms of reactivity studies.

Thus, we became interested to explore the possible isolation of titanium (I) species by applying guanidine ligands. Compared to other N-containing bidentate ligands, bulky guanidine ligands seem to be more suitable due to the possibility of varying steric bulk on the NCN moiety that may push the phenyl rings down towards each other to stabilize (to form metal-metal bond) and protect metals in unusually low oxidation states. The unusual oxidation state of +1 is known for all members of first row early transition metals except titanium, and these complexes are mainly stabilized by N-containing ligands.

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