Structure and reactivity studies of transition metals ligated by tBuSi3X (X = O, NH, N, S, and CC)

Abstract

Use of the (t)Bu(3)Si group can sterically protect O, N, S, and acetylide donors, enabling chemistry at low-coordinate transition metal centers. This article provides examples from these laboratories on the utilization of (t)Bu(3)SiO(-), (t)Bu(3)SiNH(-), (t)Bu(3)SiN(2-), (t)Bu(3)SiS(-) and (t)Bu(3)SiCC(-) as ligands in exploratory synthesis and reactivity studies of transition metal complexes.

Novel Alkoxide Cluster Topologies Featuring Rare Seesaw Geometry at Transition Metal Centers

“…The properties and the reactivity of alkoxide-ligated metal centers depend on the steric and electronic properties of the alkoxide. [12][13][14][15] Bulky ligands have been employed in low-coordinate complexes containing a plethora of different transition metals, many of which have shown small molecule activation capabilities. [16][17][18][19][20][21][22][23][24][25][26] The majority of previously reported bulky alkoxide ligands contain three identical substituents.…”

Role of Siloxides in Transition Metal Chemistry and Homogeneous Catalysis

“…[8] In 3 ML (L = CO, PMe 3 )] compounds have been stabilized with the help of silox. [8,15] A striking example is (tBu 3 SiO) 3 Ta, a relatively stable monomeric tantalum(III) siloxide obtained from reduction of (tBu 3 SiO) 3 TaCl 2 with sodium amalgam. [16] The reduction is proposed to proceed via Ta IV , through the formation of the dichloride-bridged [(tBu 3 SiO) 3 Ta] 2 (μ-Cl) 2 , which instantly disproportionates into (tBu 3 SiO) 3 Ta and (tBu 3 SiO) 3 TaCl 2 as a result of steric strain caused by the bulky silox groups (Scheme 3).…”

The Syntheses and Crystal Structures of the First Disiloxane‐1,3‐dithiol and Its Cadmium Complex

“…[8][9][10][11][12][13][14][15][16][17][18][19] More-peculiar compounds such as six-coordinate silicon complexes with sulfur ligands and increased stability in the presence of water have also been reported. Such protection allows the isolation of relatively stable, molecular compounds with -OH/SH functional groups attached directly to silicon atoms.…”

“…However, silicon chalcogenides have been applied as reagents in organic syntheses, [30,31] and metal complexes with silyl chalcogenolate ligands have been used as precursors of metal chalcogenide nanoparticles. [36][37][38][39][40] Sulfur analogs of Si-O species include cyclosilthianes, [7,[41][42][43][44][45][46][47][48] silanethiols (characterized mainly as their metal salts), [8,15,16,[36][37][38][39][40][49][50][51][52][53][54][55][56][57][58][59][60] silanedithiols, [14,61,62] silyl sulfides, [63][64][65] di-and polysulf-ides, [66][67][68][69][70] and other rare species. [33]…”