Schwefeldiimide mit Organoelement‐Substituenten der 5. Hauptgruppe

Abstract

Das Salz K,SN, (1) reagiert in Acetonitril-Suspension bei -40°C mit Diorganylelementhalogeniden R,EX (E = P, As, Sb, Bi; X = CI oder Br) zu neuen Schwefeldiimiden S(N -ER,),. In der Reihe der terr-Butylverbindungen S(N-EtBu& (E = P (2b). As (3b), Sb (4b) und Bi (5b)) ist 3 b am bestindigsten; 5 b zersetzt sich unter Normalbedingungen. Weiterhin wurden die Arsenderivate S(N -AsR2)2 mit R = Methyl (3a), Cyclohexyl (3c) und Phenyl (3d) dargestellt. Die 1R-, NMR-und Massenspektren werden diskutiert. Sulfur Diimides Containing Organoelement Substituents of Main Group 5A suspension of the salt K2SN2 (1) in acetonitrile reacts with diorgano-element halides R,EX (E = P, As, Sb, Bi; X = CI or Br) at -40°C to give new sulfur diimides, S(N-ER,),. The arsino derivative 3 b is the most stable member of the series of tert-butyl compounds, S(N-EtBu& (E = P (2b), As (3b), Sb (4b). and Bi (Sb)), while 5 b decomposes under ambient conditions. The arsino derivatives S(N-AsR2), with R = methyl (3a), cyclohexyl (3c), and phenyl(3d) have also been prepared. The IR-, NMR-, and mass spectra are discussed.Substituierte Schwefeldiimide S(NR), mit R = Alkyl-, Aryl-und Sulfonyl-Resten sind in gro-Oer Zahl bekannt'.,); sie leiten sich formal von dem in freier Form nicht bestandigen Schwefeldiimid, S(NH),, ab. Schwefeldiimide mit Organoelement-Substituenten wurden vor allem von Elementen der 4. Hauptgruppe erhalten; so existiert die vollstandige Reihe S(N -EMe,), (E = C, Si, Ge, Sn, Pb) 3). Die Verbindungen rnit Organoelement-Substituenten der 6. Hauptgruppe beschrlnken sich derzeit auf die Sulfenylderivate S(N -SR),4-6). Schwefeldiimide rnit Organoelement-Substituenten der 5 . Hauptgruppe, S(N -ER,),, wurden bisher nicht beschrieben; es gibt Chem.

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

“…Based on these values the equilibrium conformer composition at 293 K for 3 is 78% gZZg, 11% gZEg a , 6% gZEg s and 5% gZEs, and this is in line with the one found for Ph-S-N=S=N-S-Ph (2) which is 89% Z,Z and 11% Z,E [10]. At room temperature gZZg will clearly be the dominant form in solution, which is consistent with the experimental vibrational frequencies of the N=S=N fragment in 3 [23] which fit best to the values calculated for the Z,Z isomer (Table 2).…”

“…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. If so, the configurational preference of 1 would be different from that of its Group-16 analogue Ph-S-N=S=N-S-Ph (2, Figure 2), of which the Z,Z isomer is the main (about 90%) component in solution [10].…”

MOVPE growth of Ga(AsBi)/GaAs using different metalorganic precursors

“…In 1975 the first preparation of TTBBi was mentioned by Schumann and Breunig [15] and slightly better yields could be achieved by Herberhold et al [16]. The yield is more than doubled via our preparation method.…”

“…The synthesis is based on the method described by Herberhold et al [16]. 7.25 g Mg powder (298 mmol) was suspended in 200 mL Et 2 O.…”

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

“…-'H-NMR: <3 = 7,45-7,80 (m. br) (Q,H S ); 13 C-NMR: 6 = 129,8 und 133,0 (C2/C6 oder C3/C5), 134,9 (C4), 139,6 (Cl), 215,1 (CO eq ), 220,9 (CO ax ) ppm. -MS: m/e = 502 (M + ).Die zu Vergleichszwecken benötigten Bis-(diorganylstibino)schwefeldiimide, R 2 Sb(NSN)SbR : (R = r Bu[19], Ph), wurden durch Umsetzung von R.SbCl mit dem Salz K 2 SN 2 (2:1) in Acetonitril bei -40 °C erhalten:'Bu,Sb(NSN)Sb'Bu^, gelborange Kristalle, Zers. 70 °C (vgl [19]…”