Reactivity of tetrakisdimethylamido-titanium(iv) and -zirconium(iv) with thiols

Syntheses, Structures, and Properties of Trinuclear Copper(I)/Titanium(IV) Thiolate Complexes

“…In this respect, it is interesting to note that titanium sulfide films produced by CVD processes with substrate temperatures below 800°C are usually found to be amorphous. [3,[6][7][8] In addition, we found that the positions of the broad peaks (marked by an asterix) are similar to those reported for some LiTiO 2 phases. [45,46] However, this would require reduction of Ti 4+ to Ti 3+ and the presence of distinct amounts of moisture and the presence of oxygen should also lead to the formation of PhSSPh which was not found in the cleavage products.…”

“…[3] Thiol adducts of the type [TiC1 4 (HSR) 2 ] (R = c-C 6 H 11 or c-C 5 H 9 ) were found to afford bronze colored films of polycrystalline TiS 2 in CVD experiments (200-600°C, at 0.1 Torr). [4,5] [8] which led to the formation of films of TiS 2 . Thermal decomposition experiments on heteronuclear copper titanium thiolato complexes have not been reported so far.…”

“…The molecular structure of the cluster anion [Cu 2 Ti(SPh) 8 ] 2-in 1 is shown in Figure 1. There is an inversion center at the titanium atom, and 1 can be viewed as consisting of a distorted octahedral titanium atom sharing parallel trigonal faces with two copper [Cu (1) [21] however, suggest that there is no evidence for d 10 Ǟd 0 dative bonding interactions in these compounds.…”

“…Examples include [Li(OEt 2 ) 3 ][Ti(S-2,4,6-iPr 3 C 6 H 2 ) 4 ], [11] [NMe 2 H 2 ][Ti 2 -(SMe) 9 ], [Ti 3 (SMe) 12 ], [12] [Ti{S-1,3,4,6-C 6 H(CH 3 ) 4 } 4 ], [13] [NEt 4 ] 2 [Ti(SPh) 6 ], [14] [Li(C 4 H 8 O) 4 ][Ti 2 (SPh) 9 ], [15] [NH 2 9 ], [7] and [NH 2 Et 2 ] 2 [Ti(SC 6 F 5 ) 6 ], some of them isolated only in low yields. [8] [ Interest in the combination of an early and a late transition metal in a heterobimetallic complex arises because the combination of two different metal atoms, which are electrondeficient and electron-rich, respectively, offers the possibility of Lewis acid activation of a substrate molecule bound to the electron-rich metal center. Thiolato-bridged titanium heterometallic compounds have been featured in reviews over the last two decades.…”

“…[1] Interest in titanium thiolate compounds arises from the fact that such compounds can serve as single-source precursors for the formation of thin films of titanium sulfides by chemical vapor deposition (CVD). [2,[3][4][5][6][7][8] Titanium disulfide is also of interest since Whittingham first demonstrated fast, reversible Li insertion into TiS 2 over the solid solution range 0 Յ x Յ 1 of Li x TiS 2 . [9,10] However, only a few homoleptic titanium complexes with monodentate thiolato ligands have been characterized by single-crystal X-ray to date.…”