Darstellung des Stibinoschwefeldiimid-Achtrings ^tBuSb(NSN)₂Sb^tBu und einiger seiner Carbonylmetall-Derivate / Synthesis of the Eight-Membered Stibino-Sulfur Diimide Ring ^tBuSb(NSN)₂Sb^tBu and Some of its Carbonylmetal Derivatives

Abstract

<jats:title>Abstract</jats:title><jats:p> The first antimony-sulfur-nitrogen heterocycle, <jats:sup>t</jats:sup>BuSb(NSN)<jats:sub>2</jats:sub>Sb<jats:sup>t</jats:sup>Bu (1b)**, has been prepared from the reaction of <jats:sup>t</jats:sup>BuSbCl<jats:sub>2</jats:sub> with the salt K<jats:sub>2</jats:sub>SN<jats:sub>2</jats:sub>. It forms stable chelate complexes of the type (CO)<jats:sub>4</jats:sub>M[<jats:sup>t</jats:sup>BuSb(NSN)<jats:sub>2</jats:sub>Sb<jats:sup>t</jats:sup>Bu] (M = Cr (3b), Mo (4b), W (5b)). The pentacarbonylchromium complex (CO)<jats:sub>5</jats:sub>Cr[<jats:sup>t</jats:sup>BuSbCl<jats:sub>2</jats:sub>] reacts with K<jats:sub>2</jats:sub>SN<jats:sub>2</jats:sub> to give the mononuclear derivative (CO)<jats:sub>5</jats:sub>Cr[<jats:sup>t</jats:sup>BuSb(NSN)<jats:sub>2</jats:sub>Sb<jats:sup>t</jats:sup>Bu] (2b) containing the eight-membered ring 1b, whereas the corre-sponding complexes (CO)<jats:sub>5</jats:sub>Cr[R<jats:sub>2</jats:sub>SbCl] (R = <jats:sup>t</jats:sup>Bu, Ph) are converted into binuclear sulfur diimide derivatives (CO)<jats:sub>5</jats:sub>Cr[R<jats:sub>2</jats:sub>Sb(NSN)SbR<jats:sub>2</jats:sub>]Cr(CO)<jats:sub>5</jats:sub> (R = <jats:sup>t</jats:sup>Bu (6b). Ph (7b)). The new stibino-sulfur diimides 1b-7b have been characterized by IR and NMR (<jats:sup>1</jats:sup>H and <jats:sup>13</jats:sup>C) spectroscopy.</jats:p>

Novel Stibano Amines: Synthesis and Reactivity towards Group 13 Element Organics

“…Three compounds with the common formula tBu 2 SbR are described by Scherer and Janssen [R = NMe 2 , N(SiMe 3 ) 2 , N(AstBu 2 )(SiMe 3 )] and two are reported by Herberhold (R = N=S=O, N=S=NSbtBu 2 ). [3,4] …”

Syntheses, structures and DFT study of [W(CO)5(Ph2SbX)] X=Cl, Br, I

“…The inspection of their crystal structures and theoretical calculations allow to study the effect of coordination on the geometry of the R 2 SbX unit. Several complexes of this type have been synthesised [1][2][3][4][5]; none of them was studied by X-ray diffraction. We chose the series [W(CO) 5 (Ph 2 SbX)], X = Cl (1), Br (2) and I (3) for an inspection of the crystal structures and selected 1 for a study at the DFT level.…”

Structures and spectroscopic properties of sulfur-nitrogen-pnictogen chains: R2P–N S N–PR2 and R2P–N S N–AsR2

“…Structures in which R and R' are alkyl, aryl and organoelement substituents from Groups 14, 15 and 16 have been described and our own work on compounds with R = R' = SAr, SeAr has led to greater insight into the structural chemistry of such shorter chains [10][11][12]. What makes the chain compounds in which atoms of Group 15 are bonded to the nitrogen atoms of the sulfur diimide fragment particularly interesting is the fact that they can easily form transition metal complexes and a considerable number of mononuclear (chelate) and binuclear derivatives of R2X-N=S=N-XR2 (X = P, As, Sb and R = Me, t Bu, Ph) have been reported [13][14][15][16][17][18][19][20][21][22]; four of these have been structurally characterized using XRD [13][14][15][16][17]. The most studied compound in this group has been 1,1,5,5-tetra-tert-butyl-3-thia-2,4-diaza-1,5-diphospha-2,3-pentadiene [ t Bu2P-N=S=N-P t Bu2 (1), Figure 2] [23] of which the configuration in solution was investigated using NMR spectroscopy [24,25]: by comparing 15 N and 31 P chemical shifts of a set of reference compounds with the values found for 1, Herberhold et al derived that this compound primarily exists in a dynamic equilibrium of rapidly interconverting Z,E and E,Z isomers.…”