A bicyclic hydrazodiphosphine

Abstract

ALTHOUGH a few examples of aminophosphine ring atoms have been described. We now report the compounds are known only one example of a preparation of the phosphorus analogue of this polycyclic, or cage, compound is reported, namely, latter compound. P,(NMe),.ly2 Recently the arsenic a n a l ~g u e ~-~ Tris-( 1,2-dimethy1hydrazino)diphosphine (2,3,5,and another cage structure, As,(NMe),,' in which 6,

Versatile Reactivity of Cyclic 1,2-Dimethylhydrazinodiphosphines

“…of N , N ′‐dimethylhydrazine dihydrochloride with 2 equiv. of tris(dimethylaminophosphine), as previously reported . However, we slightly modified this method, by using toluene instead of benzene, and the prior extraction with pentane facilitates the sublimation step.…”

“…Cage‐like phosphorus derivatives possess interesting properties as ligands in homogeneous catalysis . Among them, the cage ligand tris(1,2‐dimethylhydrazinodiphosphine) P(NMeNMe) 3 P is known since a long time , . A few symmetrical complexes of P(NMeNMe) 3 P have been reported, concerning BH 3 ,, W(CO) 5 and Ni(CO) 3 ,, Fe(CO) 4 , and Al(Et) 3 .…”

“…Among them, the cage ligand tris(1,2‐dimethylhydrazinodiphosphine) P(NMeNMe) 3 P is known since a long time , . A few symmetrical complexes of P(NMeNMe) 3 P have been reported, concerning BH 3 ,, W(CO) 5 and Ni(CO) 3 ,, Fe(CO) 4 , and Al(Et) 3 . However, this ligand has not generated a wide attention for decades, until its first use as ligand for catalysis, in the Karash addition of bromotrichloromethane to olefins .…”

Trichonnethylphosphonsäuredihydrazid und 3.6-Bi8(trichlormethyl)-3.6-dioxo-1.2.4.5-tetraaza-3.6-diphosphacyclohexan / Trichloromethylphosphonic Acid Dihydrazide and 3,6-Bis(trichloromethyl)-3,6-dioxo-1,2,4,5-tetraaza-3,6-diphosphacyclohexane

“…[1][2][3][4][5]). Auch andere Arbeitsgruppen haben sich mit dieser Substanzklasse beschäftigt und entsprechende Verbindungen, die zwei Hydrazineinheiten im Sechsring enthalten und Derivate der phosphorigen Säure oder von Phosphonsäuren sind dargestellt [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24]. In einigen Fällen wurden ungewöhnliche Ringkonformationen beobachtet (Twistform bei 3.6-cis-Substitution) [4,25] [5]) entspricht recht genau derjenigen, die bei dem Verbindungspaar CCl3-P(=0)(0C2H5)2 und C2H50-P( = 0)(0C2H5)2 gefunden wird (<5 = 6,5 bzw.…”

Phosphorus-31 NMR of some bicyclic phosphorus compounds

“…One of these phosphorus atoms, as in is a phosphine, but an aminophosphine now occupies the second bridgehead position. Two other bicyclic cage compounds having aminophosphine bridgeheads which have been reported are _3_ ( 6 ) and _6_ {7 ). Structural data for _2_ ( 8 ), its dioxide ( 9), and its bis(phenylimide)derivative (lO), reveal a geometry for nitrogen which is intermediate between pyramidal and planar while 7 and _8_ contain nitrogens having the planar geometry observed in the majority of aminophosphines (ll).…”