Die Titelverbindungen entstehen bei der Einwirkung der silylierten Phosphanimine Me3SiNPR3 (R = CH3, C2H5) auf CrCl2(THF)2, PdCl2 und CuCl2 in Dichlormethan‐Suspension. Die drei Donor‐Acceptor‐Komplexe werden durch ihre IR‐Spektren und durch Kristallstrukturanalysen charakterisiert. [CrCl2(Me3SiNPMe3)2]: Raumgruppe Pccn, Z = 4, Strukturlösung mit 2104 unabhängigen beobachteten Reflexen, R = 0,045. Gitterkonstanten bei −70°C: a = 1326,3; b = 1562,5; c = 1171,5 pm. In der monomeren Molekülstruktur ist das Chromatom planar in der trans‐Konfiguration von den Cl‐Atomen und den N‐Atomen der Phosphanimin‐Liganden koordiniert mit Abständen CrCl = 235,94 pm und CrN = 211,7 pm. [PdCl2(Me3SiNPEt3)2]: Raumgruppe P21/n, Z = 2, Strukturlösung mit 2412 unabhängigen beobachteten Reflexen, R = 0,031. Gitterkonstanten bei 20°C: a = 917,3; b = 1390,2; c = 1161,7 pm, β = 95,80°. In der monomeren Molekülstruktur ist das Palladiumatom planar in der trans‐Konfiguration von den Cl‐Atomen und den N‐Atomen der Phosphaniminliganden koordiniert mit Abständen PdCl = 222,9 pm und PdN = 209,5 pm. [CuCl2(Me3SiNPMe3)]2: Raumgruppe Pbca, Z = 4, Strukturlösung mit 1861 unabhängigen beobachteten Reflexen, R = 0,067. Gitterkonstanten bei −70°C: a = 1440,2; b = 1205,1; c = 1536,5 pm. Die Verbindung bildet zentrosymmetrische dimere Moleküle, in denen die Cu‐Atome über nahezu symmetrische Chlorobrücken mit CuCl‐Abständen von 231,4 pm verknüpft sind. Der Abstand CuN beträgt 196,7 pm.
Professor Hans-Georg von Schnering zum 70. Geburtstag gewidmet Inhaltsu È bersicht. [NaI(HNPPh 3 ) 3 ] (1) entsteht als gelbe, feuchtigkeitsempfindliche Kristalle als Zwischenverbindung bei der Synthese von Natrium-triphenylphosphaniminat, [NaNPPh 3 ] 6 (2), aus Ph 3 PI 2 und Natriumamid in flu È ssigem Ammoniak. Entsprechend entstehen farblose Kristalle von [SrI 2 (HNPPh 3 ) 2 (THF) 2 ] (3) aus Strontiumamid und Ph 3 PI 2 in flu È ssigem Ammoniak und anschlieûender Kristallisation des prima È r gebildeten [SrI 2 (HNPPh 3 ) 4 ] aus Tetrahydrofuran. Die Komplexe 1±3 werden hauptsa È chlich durch Kristallstrukturanalysen charakterisiert.1´0,5 THF: Raumgruppe P3c1, Z = 4, Gitterkonstanten bei 193 K: a = b = 1533,2(1); c = 2545,6(1) pm, R = 0,0417. 1 hat eine Moleku È lstruktur, in der das Natriumatom tetraedrisch von einem Iod-Atom im Abstand von 315,9 pm und von den N-Atomen der drei HNPPh 3 -Moleku È le im Abstand von 238,9 pm umgeben ist. 2´C 7 H 8 : Raumgruppe P1, Z = 1, Gitterkonstanten bei 213 K: a = 1457,1(1), b = 1484,9(1), c = 1502,7(1) pm; a = 116,32(1)°, b = 115,358(10)°, c = 93,585(14)°; R = 0,0520. 2 hat eine Moleku È lstruktur, in der die sechs Natriumatome und die sechs Stickstoff-Atome der (NPPh 3 ± )-Gruppen ein hexagonales Prisma mit angena È herter D 3d -Symmetrie bilden. 3´2 THF: Raumgruppe P1, Z = 2, Gitterkonstanten bei 193 K: a = 1042,9(1), b = 1337,4(1), c = 2095,1(1) pm; a = 90,130(8)°, b = 96,310(8)°, c = 111,985(8)°; R = 0,0310. 3 hat eine Moleku È lstruktur, in der das Strontium-Atom oktaedrisch von den einander paarweise gegenu È berstehenden Iod-Atomen, von den N-Atomen der Phosphanimin-Moleku È le und von den Sauerstoff-Atomen der Tetrahydrofuran-Moleku È le koordiniert ist. Crystal Structures of the Phosphaneimine Complexes [NaI(HNPPh 3 ) 3 ] and [SrI 2 (HNPPh 3 ) 2 (THF) 2 ], as well as of Sodium Triphenylphosphoraneiminate [NaNPPh 3 ] 6Abstract. [NaI(HNPPh 3 ) 3 ] (1) has been obtained as yellow, moisture sensitive crystals as an intermediate product of the synthesis of sodium triphenylphosphoraneiminate, [NaNPPh 3 ] 6 (2) from Ph 3 PI 2 and sodium amide in liquid ammonia.Correspondingly, colourless crystals of [SrI 2 (HNPPh 3 ) 2 (THF) 2 ] (3) are formed from strontium amide and Ph 3 PI 2 in liquid ammonia and subsequent recrystallisation of the primary product [SrI 2 (HNPPh 3 ) 4 ] from thf solution. The complexes 1±3 are mainly characterized by crystal structure determinations.1´0,5 thf: space group P3c1, Z = 4, lattice dimensions at 193 K: a = b = 1533.2(1); c = 2545.6(1) pm, R = 0.0417. 1 has a molecular structure in which the sodium atom is tetrahedrally coordinated by the iodine atom with a distance of 315.9 pm and by the nitrogen atoms of the three HNPPh 3 molecules with a distance of 238.9 pm.2´C 7 H 8 : space group P1, Z = 1, lattice dimensions at 213 K: a = 1457.1(1), b = 1484.9(1), c = 1502.7(1) pm; a = 116.32(1)°, b = 115.358(10)°, c = 93.585(14)°; R = 0.0520. 2 has a molecular structure in which the six sodium atoms and the six nitrogen atoms of the (NPPh 3 ± ) groups ...
Ti3Cl8(NPMe3)3]Cl has been prepared by the reaction of TiCl3(THF)3 with Me3SiNPMe3 in dichloromethane forming green moisture sensitive crystals. According to the crystal structure determination the titanium atoms of the cation [Ti3Cl8(NPMe3)3]+ are linked by two /x3-N atoms of two NPMe3~ groups forming a distorted trigonal-bipyramidal arrangement. The third NPMe3_ group and two of the chlorine atoms have /i2-bridging functions. The mixed-valence complex [V2Cl4(NPPh3)3] is formed as dark green moisture sensitive crystals by the reaction of vanadium trichloride with Me3SiNPPh3 in boiling toluene. According to the crystal structure determination the vanadium atoms are linked by two /z2-N atoms of two NPPh3_ groups forming a nonplanar V2N2 four-membered ring with a V-V distance of 266.8(1) pm which corresponds to a (a, 1/27r) bond type. This is confirmed by the measurement of the magnetic susceptibility which leads to a magnetic moment of 1.45(5) B. M., corresponding to the remaining d 1 -electron.
Crystal Structure of the Oxophosphazene [Ph3PNPPh2NP(O)Ph2] Single crystals of [Ph3PNPPh2NP(O)Ph2] were obtained as a by‐product from the synthesis of [NaNPPh3]6 as a result of partial hydrolysis. According to the crystal structure determination the compound forms a molecular structure with a PNPNP chain with PN distances between 155.3(6) and 159.8(5) pm and PNP bond angles of 143.2(4) and 140.7(4)°. Space group P1¯, Z = 2, lattice dimensions at 213 K: a = 922.7(1); b = 1040.1(1); c = 1908.0(1) pm; α = 90.55(1)°; β = 103.01(1)°; γ = 92.87(1)°; R = 0.0859.
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