Synthesis and Structure of Titanium(III) Bis(decamethyltitanocene) Oxide

Abstract

Bis(decamethyltitanocene) oxide, [(Cp* 2 Ti) 2 O] (1; Cp* = η 5 -C 5 Me 5 ) has been obtained as a yellow crystalline solid after reacting equimolar amounts of the hydride [Cp* 2 TiH] and the hydroxide [Cp* 2 Ti(OH)]. The solid-state structure of 1 revealed a linear Ti−O−Ti arrangement and a mutual, nearly perpendicular orientation of the bent-sandwich titanocene moieties; the length of both Ti−O bonds amounted to 1.9080(3) Å. A unique structural feature was a close-to-eclipsed conformation of the cyclopentadienyl ligands, attributed to the high steric congestion of 1. The molecule in toluene glass exhibited a triplet state EPR spectrum of rhombic symmetry, having zero field splitting D = 0.02159 cm −1 and E = 0.00230 cm −1 . The 1 H NMR spectrum of 1 in toluene-d 8 displays a paramagnetic resonance at δ 4.3 ppm (Δν 1/2 ≈ 270 Hz). Compound 1 reacts with 1 molar equiv of water to give [Cp* 2 Ti(OH)]. In CD 2 Cl 2 , 1 is oxidized to yield the major product [(Cp*TiCl 2 ) 2 O] and minor product [{Cp*Ti(Cl)O} 3 ].

Examples of Different Reactions of Benzylsulfanyl‐Substituted Alkynes with Selected Complexes of TiII and CoI

“…Red crystals of 5 suitable for X-ray crystallography were obtained from n-hexane solution. [18] Re-lated uncharged metal-sulfur cubane structures [CpMS] 4 have also been reported for other transition metals like vanadium, [19] iron, [20] chromium [21] and cobalt. It shows a tetrahedral geometry, with two SBn and two Cp moieties occupying the coordination sites.…”

The Reductive Activation of CO2Across a Ti═Ti Double Bond: Synthetic, Structural, and Mechanistic Studies

“…For example, [Cp* 2 Ti] 2 (μ-S) is a green paramagnetic complex with a Ti···Ti separation of 4.7069(7) Å and a Ti–S–Ti angle of 174.37(4)°. 66 The lack of a bonding (or an antiferromagentic coupling) interaction between the two d 1 centers in [Cp* 2 Ti] 2 (μ-S) gives rise to an electronic triplet state. In contrast, both 11 and 10 are diamagnetic.…”

Ground Triplet Spirobiradical: 2,2′,7,7′-Tetra(tert-butyl)-9,9′(10H,10′H)-spirobiacridine-10,10′-dioxyl

“…The best fit curve was given with 2 J / k B = +22.8(10) K, g = 2.0054 (fixed), and zj / k B = −1.12(2) K. To the best of our knowledge, the ferromagnetic coupling is the strongest ever reported in paramagnetic spiro-junctioned compounds. − …”

“…Spiro-junctioned compounds have a unique cruciform-like structure and have been of considerable interest for application as building blocks for covalent–organic frameworks (COFs), metal–organic frameworks (MOFs), organic light-emitting diodes (OLEDs), and thermal-switching materials . In particular, the orthogonal arrangement ( D 2 d ) has attracted a great deal of attention in magnetochemistry, e.g., radical compounds − and metal complexes. , …”