Elementorganische Amin/Imin-Verbindungen, XVIII [1] Amino-Imino-Thiophosphorane: σ³, λ⁵-Phosphazene / Elementorganic Amino/Imino Compounds, XVIII [1] Aminoiminothiophosphoranes: σ³, λ⁵-Phosphazenes

Abstract

<jats:title>Abstract</jats:title><jats:p> The reaction of the aminoiminothiophosphoranes (1) with methanol yields the bisamino-thiophosphoric acid derivatives (3). la and IVb → VTb element halides form the new P-N element four membered rings 4 →7, which partially exist as a mixture of eis and trans isomers. Different ylide group transfer is observed on the reaction of la with trimethyl -phosphine or trimethyl phosphite. With trimethylphosphine (CH<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub>P(S) and a phos-pha(III)azene are formed, with trimethyl phosphite (CH<jats:sub>3</jats:sub>O)<jats:sub>3</jats:sub>P = NC(CH<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub> and the [2 + 2] cycloaddition product of la and (R<jats:sub>3</jats:sub>C)(R<jats:sub>3</jats:sub>Si)N-P = S (R = CH<jats:sub>3</jats:sub>) can be isolated.</jats:p>

Mono-, Di-, and Tricoordinated Phosphorus Attached to a N−N Unit: An Experimental and Theoretical Study

“…The synthesis of PN species containing a two-coordinated phosphorus(III) atom such as the iminophosphanes, R 2 N−PNR, can be achieved by (i) 1.2 elimination, (ii) substitution reaction starting from a known iminophosphane, (iii) conversions 5 for example, by a 1.3 shift of a silyl group, and (iv) ring opening, for example, by thermal treatment of λ 3 , λ 5 aza-diphosphiridines . The most convenient synthesis method seems to be the 1.2 elimination of Me 3 Si−X from aminophosphanes, which can be generated easily by reaction of PX 3 with lithium amides (eq 2, R = TMS, X = F, Cl, and Br). 3a, …”

Crystal structure ofO-isopropyl [bis(trimethylsilyl)amino](tert-butylamino)phosphinothioate

“…For details of the synthesis of [bis(trimethylsilyl)amino](tertbutylimino)thiophosphorane, see: Scherer & Kuhn (1974). For its chemical reactivity, see: Kovalenko et al (2011aKovalenko et al ( ,b,c, 2012; Rusanov et al (1992); Scherer et al (1978). For its applications in catalysis, see: Zhao et al (2014a,b); Goldys & Dixon (2014); Samuel et al (2014); Kawalec et al (2012); Zhang et al (2007).…”

“…R[F 2 > 2(F 2 )] = 0.041 wR(F 2 ) = 0.115 S = 1.08 7436 reflections 184 parameters H atoms treated by a mixture of independent and constrained refinement Á max = 0.84 e Å À3 Á min = À0.34 e Å À3 Table 1 Hydrogen-bond geometry (Å , ). Kuhn in 1974, see: Scherer &Kuhn (1974), and later some general chemical reactivity of this compound was studied, see: Scherer et al (1978). Based on these early results, pentavalent tricoordinated σ 3 λ 5 -phosphoranes recommended themselves as promising ligands for the obtaining of new organometallic metallacycles with specific features.…”