Elementorganische Amin/Imin‐Verbindungen, XVI. Neue Diazadiphosphetidine

Abstract

P-Methyldiazadiphosphetidine des Typs 2 und 5 entstehen durch Umsetzung eines Phosphatriazens mit Dichlormethylphosphin, durch Cyclisierung des Bis(tert-butylamino)methylphosphins mit Phosphorhalogeniden oder durch Grignardierung von P-Chlor-diazadiphosphetidinen. 2 und 5 lassen sich mit Chalkogenen zu den Diazadiphosphetidin-mono-und dichalkogeniden 6 und 7 (X = 0 + Te), durch Trimethylsilylazid zum Diazadiphosphetidin-diimid 7e oxidieren. Mit Methylhalogeniden bilden 2 und 5 die cyclischen Phosphoniumsalze 8 und 9. 2 und AICI, ergeben das erste 1,3,2,4-Diazadiphosphetidin-2-ylium-Salz 12, eine Phosphor-Stickstoff-Verbindung bei der ein Phosphoratom zweifach koordiniert ist. Elementorganic Amine/Imine Compounds, XVI I' New Diazadip4osphetidinesThe P-methyldiazadiphosphetidines 2 and 5 are formed by the reaction of a phosphatriazene with dichloromethylphosphine, by cyclization of the bis(rerr-buty1amino)methylphosphine with phosphorus halides or by Grignard reaction of P-chloro-diazadiphosphetidines. 2 and 5 can be oxidized to the diazadiphosphetidine-mono-and -dichalcogenides 6 and 7 (X = 0 -+ Te). trimethylsilvlazide oxidizes 5 to the diazadiphosphetidine-diimide 7e. With methylhalides 2 and 5 form the cyclic phosphonium salts 8 and 9. 2 and AICI, yield the first 1,3,2,4diazadiphosphetidine-2-ylium salt 12, a phosphorus nitrogen compound in which one phosphorus atom has the coordination number two. ~ ~~Diazadiphosphetidine (XPNR)2 sind bislang nur an Hand solcher Beispiele beschrieben, bei denen X einen Liganden mit mindestens einem ,,freien" Elektronenpaar darstellt *).Von den wenigen bekannten Verbindungen wurde beim (CIPNC4H9-t), 3*4) erstmals die Isomerenform (cis-Isomeres) durch eine Rontgenstrukturanalyse ? bestimmt. Neuerdings wird dieser Substanzklasse auch in bindungstheoretischer Hinsicht starkes Interesse entgegengebracht 'I. ') XV. Mitteil.: 0.

Activation of Small Molecules by Phosphorus Biradicaloids

“…Depending on the stoichiometry, the amount and kind of base, solvent, temperature, etc., the reaction can be carried out stepwise either via aminobis(dichloro)phosphanes or aminodichlorophosphanes. [40][41][42][43][44][45][46][47][48][49][50][51][52][53][54][55][56] These reactions can be referred to as base-induced sequential dehydrochlorination or, in general, as cyclocondensation processes.…”

“…In the literature there are only a few reports on the oxidation of 1,3‐dichloro‐ cyclo ‐1,3‐diphospha(III)‐2,4‐diazanes ( 1 R) with O 2 ,87 S 8 ,88 and Se x 89 (Scheme ), which, however, did not lead to the formation of dichalcogen bridged species but to complete oxidation of both P atoms to four‐coordinated P V compounds. To our knowledge, there is only one example in which such an oxidation was successfully carried out with tellurium (Scheme ) 55. Recently, Woollins, Chivers, Karaghiosoff, and co‐workers reported the first solid‐state structural characterizations of Te m (RP) n rings including Te 3 (PR) 3 , Te(PR) 2 (R=OMes*), and Te(PR) 3 (R=Ad), Te(PR) 4 (R=Fc); and P V 2 N 2 ‐stabilized organophosphorus(III)‐tellurium rings 90…”

“…To our knowledge, there is only one example in which such an oxidation was successfully carried out with tellurium (Scheme 9). [55] Recently, Woollins, Chivers, Karaghiosoff, and coworkers reported the first solid-state structural characterizations of Te m (RP) n rings including Te 3 (PR) 3 , Te(PR) 2 (R = OMes*), and Te(PR) 3 (R = Ad), Te(PR) 4 (R = Fc); and P V 2 N 2 -stabilized organophosphorus(III)-tellurium rings. [90]…”

On New Staudinger Type Reactions of Phosphorus Centered Biradicaloids, [P(μ‐NR)]2 (R = Ter, Hyp), with Ionic and Covalent Azides

“…As depicted in Scheme 7, reaction of 1 Hyp with Mes*‐N 3 resulted in a completely different reaction channel leading to the formation of a cyclo‐diazaphosphetidine 4 HypMes*_ P6 (Figure 4 top, Scheme 8 corresponds to isomer P6 ) without release of molecular nitrogen. [ 71,72,81,82,73–80 ] The 31 P NMR spectrum featured two doublet resonances at 9.9 ppm for the four‐coordinate and 382.5 ppm ( 2 J [ 31 P‐ 31 P] = 39 Hz) for the two‐coordinate phosphorus atoms. With a decomposition point of 91 °C, 4 HypMes*_ P6 is thermally less stable compared to the pentadienes ( 3 HypDipp_ I2 : 122°, 3 HypTer_ I5 : 231 °C).…”

cis-Bisphenylalkynyl cyclodiphosphazane: Oxidation reactions and transition metal complexes

“…These are restricted mainly to alkyl and phenyl derivatives (I), which are prepared starting from aryl-or alkyl phosphorus dihalides (RPCl 2 ) or by some rearrangement reactions (II and III). [9] This may be due to the difficulties in the reaction of cis-[ t BuNPCl] 2 with RLi and RMgX, as these reagents are often known to cleave the P-N bonds. A few years back we synthesized the first metallocene derivative of cyclodiphosphazane (IV) [10] and reacted with cuprous halides to generate first examples of phosphine based sodalite frameworks, where the cyclodiphosphazanes act as ditopic linkers and Cu 4 X 4 clusters act as tetrahedral nodes.…”