T. Timothy Nadasdi

TL;DR: A comprehensive and systematic review of the syntheses, structures and reactivities of thiolate complexes of group 4 and 5 metals is presented in this paper, which includes a discussion of monometallic and polymetallic species as well as recent advances in heterobimetallic derivatives.

TL;DR: In this paper, the compounds [CpTi(SCH 2 -CH 2 S) 2 Cu] n and [C pTi(sCH 2 CH 2 S 2 )Cu] 2 (2) have been used as precursors to heterometallic compounds.

Abstract: The reaction of CpTiCl[sub 3] with 1,3-propanedithiol yields the mononuclear Ti(IV) species CpTi(SCH[sub 2]CH[sub 2]CH[sub 2]S)Cl (1) Reactions of (1) with various Lewis bases (thiols, water) are investigated and the products are characterized The Lewis acidity of the Ti centers is satisfied by Ti-O [tau]-bonding, which is reflected in the Ti O Ti[prime] bond angles which range from 158 to 170[degrees] Fenske-Hall MO calculations support the notion that the Lewis acidity of the Ti centers in (1) is attributable to three vacant low-lying orbitals of a[sub 1] and e symmetry The Lewis acidity is dominated by the 1e orbitals This affords either a [tau]-interaction or formal Lewis base donation in the plane parallel to the cyclopentadienyl ring Further interaction with the a[sub 1] orbital is sterically blocked, but interaction with this vacant orbital can be induced by a constrained ligand geometry 34 refs, 13 figs, 3 tabs

TL;DR: In this paper, the authors showed that CpTi(SCHCH2CH2S) with MeLi, AlMe3, or t-BuLi can be readily prepared from reaction of Cp†Ti (SCH 2 CH2S), MeCp (2), and PMe3.