Phosphoraneiminato- and phosphaneimine complexes of Nickel(II). Crystal structures of [Ni(O₃SCF₃)(NPMe₃)]₄, [Ni₄Br₅{NP(NMe₂)₃}₃], [NiBr₂{HNP(NMe₂)₃}₂], and [Ni(PMePh₂)₄]

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Krieger, Matthias ; Gould, Robert O. ; Harms, Klaus ; Greiner, Andreas ; Dehnicke, Kurt:
Phosphoraneiminato- and phosphaneimine complexes of Nickel(II). Crystal structures of [Ni(O₃SCF₃)(NPMe₃)]₄, [Ni₄Br₅{NP(NMe₂)₃}₃], [NiBr₂{HNP(NMe₂)₃}₂], and [Ni(PMePh₂)₄].
In: Zeitschrift für anorganische und allgemeine Chemie. Bd. 627 (2001) Heft 4 . - S. 747-754.
ISSN 1521-3749
DOI: https://doi.org/10.1002/1521-3749(200104)627:4<747::AID-ZAAC747>3.0.CO;2-H

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Abstract

Black-violet single crystals of Ni(O3SCF3)(NPMe3)](4) (1) have been prepared from NiBr(NPMe3)], and copper(l)triflate by metathesis reaction. The nickel atoms are associated via mu (3)-N bridges of the (NPMe3-) groups to form a heterocubane. The triflate ions are bonded to the Ni atoms in a chelate fashion. Blue single crystals of Ni4Br5{NP(NMe2)(3)}(3)] (2) are obtained by the reaction of NiBr2 with Me3SiNP(NMe2)(3) in boiling toluene in the presence of sodium fluoride. The Ni atoms in 2 are associated with three mu (3)-bridged nitrogen atoms of the (NP(NMe2)(3)(-)) groups as well as by a mu (3)-Br atom to give a distorted heterocubane. Deep blue single crystals of the phosphaneimine complex NiBr2{HNP(NMe2)(3)}(2)] (3) are formed from Me3SiNP(NMe2)(3) and NiBr2 in boiling dichloromethane. In 3 the Ni atom is tetrahedrally coordinated by the bromine atoms and by the nitrogen atoms of the phosphane imine molecules. Pale red crystals of Ni(PMePh2)(4)] (4) have been obtained by the reaction of NiBr(NPMe3)](4) with lithium phenylacetilyde in the presence of PMePh2. In 4 the Ni atom is distorted tetrahedrally coordinated by the phosphorus atoms of the phosphane molecules with Ni-P distances of 219.9 pm in average. 1-4 have been characterized by crystallographic X-ray analyses. 1: Space group P2(1)/n, Z = 4, lattice dimensions at 193 K: a = 1566.7(2): b = 1479.9(1); c = 1960,6(2) pmt beta = 105.908(9)degrees; R = 0.0443. 2 3CH(2)Cl(2): Space group P2(1)/c, Z = 4. lattice dimensions at 293 K: a = 1226.0(3); b = 1614.0(3); c = 2406.0(5) pm; beta = 92.33(3)degrees; R=0.0703. 3: Space group C2/c, Z = 4, latttice dimensions at 203 K: a = 1840.7(1); b = 810,1(1); c = 1607.2(2)pml beta = 94.74(1)degrees, R = 0.0340. 4: Space group P (1) over bar, Z = 2, lattice dimensions at 223 K: a = 1053.1(2); b = 1315.0(3); c = 1674.5(3) pm: alpha = 81.55(1)degrees; p = 79.15(2)degrees; gamma = 84.91(2)degrees; R = 0.0497.