Phosphaniminato‐Komplexe des Vanadiums Die Kristallstruktur von [V₃Cl₆(NPMe₃)₅⁺]₂[V₄O₄Cl₈(NPMe₃)₂²⁻] ·; 6 CH₃CN

Abstract

Professor Dietrich Babel zum 65. Geburtstag gewidmet Inhaltsiibersicht. Vanadiumtetrachlorid reagiert in CC14-Lijsung rnit MesSiNPMe3 unter Bildung des Donor-Akzeptorkomplexes [VCL,(Me,SiNPMe,)], der sich in siedendem Acetonitril rnit weiterem Me3SiNPMe3 zu dem Phosphaniminatokomplex [V3C16(NPMe,),] 'C1-umsetzt. Durch partielle Hydrolyse in Acetonitrillosung entstehen hieraus schwarze Einkristalle[V3C16(NPMe3)5+]2[V404Cls(NPMe3)~-] * 6CH3CN, die wir rontgenographisch charakterisiert haben. Raumgruppe P2, /c, Z = 2, Strukturlosung mit 3 008 unabhangigen beobachteten Reflexen, R = 0,090. Gitterkonstanten bei -70°C: a = 1379,O; b = 1915,8; c = 2278 pm, / 3 = 102,79". In dem komplexen Kation bilden die drei Vanadiumatome rnit zwei p3-NPMe3-Gruppen eine trigonale Bipyramide, die drei ubrigen NPMe,-Gruppen und die Chloratome sind terminal gebunden. In dem Anion [V404C18(NPMe,)2]2-sind die Vanadiumatome iiber p2-0-Atome zu einem Rechteck verknupft; zusatzlich fungieren die beiden Phosphaniminatoliganden als p2-N-Brucken. Phosphoraneiminato Complexes of Vanadiun i. The Crystal Structure of [V,CI,(NPMe,),fl,[V,O,CI,(NPMe,)~-] -6 CH ,CN Abstract. Vanadiumtetrachloride reacts in CC1, solution with Me3SiNPMe3 to form the donor acceptor complex [VC14(Me3SiNPMe3)], which reacts with excess Me,SiNPMe, in boiling acetonitrile to form the phosphoraneiminato complex [V,C&(NPMe& + Cl-. Partial hydrolysis in acetonitrile solution leads to black single crystals of [V3Cl6(NPMe3),+],-[V404Cls(NPMe3)?-] . 6CH3CN, which are characterized by a crystal structure determination. Space group P2,/c, Z = 2, structure solution with 3 008 observed unique reflections, R = 0.090. Lattice dimensions at -70°C: a = 1379.0, b = 1915.8, c = 2278 pm, p = 102,79". In the complex cation the three vanadium atoms form a trigonal bipyramid with two p3-NPMe3 groups; the residual NPMe,-groups and the chlorine atoms are in terminal functions. In the anion [V404C18(NPMe3)2]2-the vanadium atoms are linked by p2-0 atoms to form a rectangle; in addition the two phosphoraneiminato ligands form p2-N bridges.

Synthesis and Characterization of Vanadium(V)−Phosphinimide Complexes

“…[9][10][11] In addition, several groups have reported related vanadium(IV)-and vanadium(III)-phosphinimide derivatives. [12][13][14][15][16][17] In this paper, we describe our efforts to prepare and characterize V(V)-phosphinimide derivatives. A series of vanadium-imide-phosphinimide complexes are reported.…”

“…Relatively few vanadium(V)−phosphinimide complexes have been reported previously. The reactions of VOX 3 (X = Cl, F) with Me 3 SiNPR 3 have led to a variety of vanadium(V)−phosphinimide complexes such as VOCl 2 (NPPh 3 ), VOCl(NPPh 3 ) 2 , VCl 3 (NPPh 3 ) 2 , VOF 2 (NPPh 3 ), VOCl 2 (NPPh 2 NS(O)Me 2 ), VCl 2 (N(NPPh 2 ) 2 ), and VCl 2 (NP(CF 3 ) 2 NP(CF 3 )NP(CF 3 ) 2 ), − whereas reactions of V(NSiMe 3 )Cl 3 with PR 3 Cl 2 or Me 3 SiNP(C 2 F 5 ) 2 Cl resulted in the vanadium(V)−phosphinimide complexes V(NPR 3 ) n Cl 5 - n (R = Ph, n = 1−4, R 3 = MePh 2 , Me 2 Ph, n = 1) and VCl 2 (NP(C 2 F 5 ) 2 NP(C 2 F 5 )NP(C 2 F 5 ) 2 ), respectively. − In addition, several groups have reported related vanadium(IV)− and vanadium(III)−phosphinimide derivatives. − In this paper, we describe our efforts to prepare and characterize V(V)−phosphinimide derivatives. A series of vanadium−imide−phosphinimide complexes are reported.…”

Phosphaniminato-Acetato-Cluster von Kupfer und Zink. Kristallstrukturen von [Cu4(NPEt3)2(O2CCH3)6] und [Zn4(NPEt3)2(O2CCH3)6]

“…[11], Vanadium(IV) [12], Zirkonium(IV) [13] und Hafnium(IV) [13] [3,14], la È ût sich Cu(1) auch als (4 + 1)-koordiniert beschreiben. Dieses Koordinationsmuster trifft auch fu È r Cu(4) zu, da die Bindung zu dem Sauerstoffatom in der Apicalposition O(52 A) mit 225,4 pm ebenfalls dem Donor-Akzeptortyp zuzurechnen ist.…”