Phosphaniminato- und Phosphanimin-Komplexe von Nickel(II). Die Kristallstrukturen von [Ni(O3SCF3)(NPMe3)]4, [Ni4Br5{NP(NMe2)3}3], [NiBr2{HNP(NMe2)3}2] und [Ni(PMePh2)4]

Abstract

Professor Josef Goubeau in memoriamInhaltsu È bersicht. [Ni(O 3 SCF 3 )(NPMe 3 )] 4 (1) wird durch Metathese-Reaktion aus dem Phosphaniminato-Komplex [NiBr(NPMe 3 )] 4 und Kupfer(I)-triflat als schwarz-violette Kristalle erhalten. In ihnen bilden die Nickelatome und die N-Atome der (NPMe 3 ± )-Gruppen ein Heterokuban-Geru È st, wa È hrend die Triflat-Ionen u È ber je zwei O-Atome chelatartig an die Nickel-Atome koordiniert sind. Demgegenu È ber entsteht [Ni 4 Br 5 {NP(NMe 2 ) 3 } 3 ] (2) in Form blauer Kristalle durch Reaktion von Me 3 SiNP(NMe 2 ) 3 und Nickel(II)-bromid in siedendem Toluol in Gegenwart von Natriumfluorid. Die Struktur von 2 entspricht einem Heterokuban, dessen vier Nickel-Atome, drei N-Atome der Phosphaniminato-Gruppen {NP(NMe 2 ) 3 ± } und eines der Bromo-Liganden das Ni 4 N 3 Br-Geru È st bilden. Der Phosphanimin-Komplex [NiBr 2 {HNP(NMe 2 ) 3 } 2 ] (3) entsteht als tiefblaue Kristalle aus Me 3 SiNP(NMe 2 ) 3 und NiBr 2 in siedendem Dichlormethan. In 3 ist das Nickel-Atom verzerrt tetraedrisch von zwei Bromo-Liganden und den N-Atomen der beiden Phosphanimin-Moleku È le umgeben. [Ni(PMePh 2 ) 4 ] (4) erhielten wir bei Versuchen zur Substitution der Brom-Atome von [NiBr(NPMe 3 )] 4 mittels Lithiumphenylacetylid in Gegenwart von PMePh 2 als hellrote Kristalle. In 4 ist das Nickel-Atom verzerrt tetraedrisch von den Phosphor-Atomen der Phosphan-Moleku È le mit Ni±P-Absta È nden von im Mittel 219,9 pm koordiniert. 1±4 werden durch ro È ntgenographische Strukturanalysen charakterisiert.1: Raumgruppe P2 1 /n, Z = 4, Gitterkonstanten bei 193 K: a = 1566,7(2); b = 1479,9(1); c = 1960,6(2) pm; b = 105,908 (9)°; R = 0,0443. 2´3 CH 2 Cl 2 : Raumgruppe P2 1 /c, Z = 4, Gitterkonstanten bei 293 K: a = 1226,0(3); b = 1614,0(3); c = 2406,0(5) pm; b = 92,34(3)°; R = 0,0703. 3: Raumgruppe C2/c, Z = 4, Gitterkonstanten bei 203 K: a = 1840,7(1); b = 810,1(1); c = 1607,2(2) pm; b = 94,74(1)°, R = 0,0340. 4: Raumgruppe P1, Z = 2, Gitterkonstanten bei 223 K: a = 1053,1(2); b = 1315,0(3); c = 1674,5(3) pm; a = 81,55(1)°; b = 79,15(2)°; c = 84,91(2)°; R = 0,0497. Abstract. Black-violet single crystals of [Ni(O 3 SCF 3 )-(NPMe 3 )] 4 (1) have been prepared from [NiBr(NPMe 3 )] 4 and copper(I)triflate by metathesis reaction. The nickel atoms are associated via l 3 -N bridges of the (NPMe 3 ± ) groups to form a heterocubane. The triflate ions are bonded to the Ni atoms in a chelate fashion. Blue single crystals of [Ni 4 Br 5 {NP(NMe 2 ) 3 } 3 ](2) are obtained by the reaction of NiBr 2 with Me 3 SiNP(NMe 2 ) 3 in boiling toluene in the presence of sodium fluoride. The Ni atoms in 2 are associated with three l 3 -bridged nitrogen atoms of the (NP(NMe 2 ) 3 ± ) groups as well as by a l 3 -Br atom to give a distorted heterocubane. Deep blue single crystals of the phosphaneimine complex [NiBr 2 {HNP(NMe 2 ) 3 } 2 ] (3) are formed from Me 3 SiNP(NMe 2 ) 3 and NiBr 2 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...

Stereochemistry and Spin State in Four-Coordinate Transition Metal Compounds

“…Finally, the d 10 configuration (Figure ) is expected from the calculations to give essentially tetrahedral complexes. All structurally characterized homoleptic complexes with this electron configuration (Table ) appear to be nearly perfect tetrahedra, the most distorted one being [Ni(PMePh 2 ) 4 ], with a distortion of a 17% toward the square. A remarkable exception is the highly distorted tetrahedral structure of the [CuD 4 ] 3− anion in Ba 7 (CuD 4 ) 3 D 5 (φ T→SP = 30%) that results in a surprisingly short D−D distance worthwhile of a deeper structural investigation.…”

14 Iron, cobalt and nickel

“…In the presence of [NiBr 2 (dppe)] and zinc powder, 7-oxabenzonorbornadienes react with propiolates forming benzocoumarin derivatives in a high-yield one-pot synthesis with high regio-and stereo-selectivity 81. In addition to distorted tetrahedral[Ni(PMePh 2 ) 4 ], tetrahedral [NiBr 2 (HNP(NMe 2 ) 3 ) 2 ]; [Ni(O 3 SCF 3 )(NPMe 3 )] 4 (cubane)and [Ni 4 Br 5 (NP(NMe 2 ) 3 ) 3 ] 4 (distorted heterocubane) have been described 82.…”