Crystal structures of the phosphoraneiminato complex [INi(NPMe₃)]₄ · C₄H₈O · C7H₈ and of the phosphanimine complex [INi{Me₂Si(NPMe₃)₂}(HNPMe₃)]⁺I⁻

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Müller, Ulrich ; Bock, Oliver ; Sippel, Heike ; Gröb, Thorsten ; Dehnicke, Kurt ; Greiner, Andreas:
Crystal structures of the phosphoraneiminato complex [INi(NPMe₃)]₄ · C₄H₈O · C7H₈ and of the phosphanimine complex [INi{Me₂Si(NPMe₃)₂}(HNPMe₃)]⁺I⁻.
In: Zeitschrift für anorganische und allgemeine Chemie. Bd. 628 (2002) Heft 7 . - S. 1703-1707.
ISSN 1521-3749
DOI: https://doi.org/10.1002/1521-3749(200207)628:7<1703::AID-ZAAC1703>3.0.CO;2-3

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Abstract

The phosphoraneiminato complex 1Ni(NPMe3)](4) was obtained by reaction of NiI2 in molten Me3SiNPMe3 in the presence of potassium fluoride at 200degreesC. Dark-green single crystals of INi(NPMe3)](4) (.) C4H8O (.) C7H8 were formed from THF-toluene solution. According to the X-ray crystal structure determination the complex has a Ni4N4 heterocubane core and its symmetry deviates only marginally from T-d (space group Pca2(1), Z = 4, a = 3160.7(6), b = 1001.5(1), c = 1422.6(8) pm). The INi(NPMe3)](4) molecules are stacked to columns parallel to b, with a nearly tetragonal pattern in projection on (010). The solvent molecules reside in channels between the columns. A side product of the synthesis were blue single crystals of the phosphanimine complex INi{Me2Si(NPMe3)(2)}(HNPMe3)]I-+(-). The crystal structure determination (space group Pca2(1), Z = 4, a = 1213.3(4) b - 1582.7(6), c = 1339.7(4) pm) revealed a distorted tetrahedral coordination of the Ni atom in the cation; the coordinated atoms are the two N atoms of the chelating bis(phosphane)imine molecule, the N atom of the phosphaneimine molecule HNPMe3 and one iodo ligand.