ISSN:
0044-2313
Keywords:
Phosphorane Iminato Complexes of Aluminium, Gallium and Antimony, Syntheses, Crystal Structures
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Syntheses and Crystal Structures of the Phosphorane Iminato Complexes [MCl2(NPPh3)]2 with M = Al and Ga, [SbCl2(NPMe3)(DMF)]2, and of the Phosphorane Imine Complex [Ph3PNH · BF3] · THFThe phosphorane iminato complexes [MCl2(NPPh3)]2 with M = Al and Ga and [SbCl2(NPMe3)(DMF)]2 are formed as colourless crystals by reactions of the anhydrous trichlorides MCl3 (M = Al, Ga, Sb) with the corresponding silylated phosphorane imines Me3SiNPR3 in acetonitrile and in dimethyl formamide, respectively. The phosphorane imine derivative [Ph3PNH · BF3] · THF is formed from Me3SiNPPh3 and boron trifluoride etherate in boiling tetrahydrofuran. The compounds are characterized by their i. r. spectra and by crystal structure analyses.[AlCl2(NPPh3)]2: Space group P1, Z = 1, structure solution with 1 585 observed unique reflections, R = 0.061. Lattice dimensions at -70°C: a = 917.6, b = 1 053.5, c = 1 145.2 pm, α = 111.72°, β = 100.80°, γ = 109.95°.[GaCl2(NPPh3)]2: Space group P1, Z = 1, structure solution with 2 586 observed unique reflections, R = 0.066. Lattice dimensions at -70°C: a = 917.5, b = 1 058.3, c = 1 153.7 pm, α = 105.52°, β = 107.75°, γ = 109.88°.In both compounds the metal atoms are linked to planar M2N2 four-membered rings via the N-atoms of the phosphorane iminato groups.[SbCl2(NPMe3)(DMF)]2: Space group P21/n, Z = 4, structure solution with 3 805 observed unique reflections, R = 0.038. Lattice dimensions at -70°C: a = 1 913.0, b = 726.8, c = 2 040.7 pm, β = 113.62°. The unit cell contains two symmetry independent dimeric molecules, in which the antimony atoms are centrosymmetricly μ2 linked via the N-atoms of the phosphorane iminato groups. Along with the oxygen atom of the dimethyl formamide molecule the Sb atoms achieve a ψ-octahedral environment.[Ph3PNH · BF3] · THF: Space group C2/c, Z = 8, structure solution with 2 048 observed unique reflections, R = 0.058. Lattice dimensions at -70°C: a = 2 460.4, b = 869.2, c = 1 978.0 pm, β = 116.35°.
Notes:
Die Phosphaniminatokomplexe [MCl2(NPPh3)]2 mit M = Al und Ga und [SbCl2(NPMe3)(DMF)]2 entstehen bei Reaktionen der wasserfreien Trichloride MCl3 (M = Al, Ga, Sb) mit den entsprechenden silylierten Phosphaniminen Me3SiNPR3 in Acetonitril bzw. in Dimethylformamid als farblose Einkristalle. Das Phosphanimin-Derivat [Ph3PNH · BF3] entsteht aus Me3SiNPPh3 und Bortrifluorid-Etherat in siedendem Tetrahydrofuran. Die Verbindungen werden durch ihre IR-Spektren und durch Kristallstrukturanalysen charakterisiert.[AlCl2(NPPh3)]2: Raumgruppe P1, Z = 1, Strukturlösung mit 1 585 beobachteten unabhängigen Reflexen, R = 0,061. Gitterkonstanten bei -70°C: a = 917,6; b = 1 053,5; c = 1 145,2 pm; α = 111,72°; β = 100,80° γ = 109,95°.[GaCl2(NPPh3)]2: Raumgruppe P1, Z = 1, Strukturlösung mit 2 586 beobachteten unabhängigen Reflexen, R = 0,066. Gitterkonstanten bei -70°C: a = 917,5; b = 1 058,3; c = 1 153,7 pm; α = 105,52°; β = 107,75°; γ = 109,88°. In beiden Verbindungen sind die Metallatome über die N-Atome der Phosphaniminatogruppen zu planaren M2N2-Vierringen verknüpft.[SbCl2(NPMe3)(DMF)]2: Raumgruppe P21/n, Z = 4, Strukturlösung mit 3 805 beobachteten unabhängigen Reflexen, R = 0,038. Gitterkonstanten bei -70°C: a = 1 913,0; b = 726,8; c = 2 040,7 pm; β = 113,62°. Die Elementarzelle enthält zwei symmetrieunabhängige dimere Moleküle, in denen die Antimonatome zentrosymmetrisch ψ2 über die N-Atome der Phosphaniminatogruppen verknüpft sind. Zusammen mit dem O-Atom des Dimethylformamid-Moleküls erreichen die Sb-Atome ψ-oktaedrische Umgebung.[Ph3PNH · BF3] · THF: Raumgruppe C2/c, Z = 8, Strukturlösung mit 2 048 beobachteten unabhängigen Reflexen, R = 0,058. Gitterkonstanten bei -70°C: a = 2 460,4; b = 869,2; c = 1 978,0 pm; β = 116,35°.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19956210319
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