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)]

Black-violet single crystals of [Ni(O3SCF3)(NPMe3)](4) (1) have been prepar ed from [NiBr(NPMe3)], and copper(l)triflate by metathesis reaction. The ni ckel atoms are associated via mu (3)-N bridges of the (NPMe3-) groups to fo rm a heterocubane. The triflate ions are bonded to the Ni atoms in a chelat e fashion. Blue single crystals of [Ni4Br5{NP(NMe2)(3)}(3)] (2) are obtaine d 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) ha ve been obtained by the reaction of [NiBr(NPMe3)](4) with lithium phenylace tilyde in the presence of PMePh2. In 4 the Ni atom is distorted tetrahedral ly 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 crystallo graphic 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=0.07 03. 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.