Synthese und Kristallstrukturen der Phosphanimin-Komplexe [Cu(μ-HNPEt3)]4(O3S-CF3)4 und [Pt2Me6(μ-I)2(μ-HNPMe3)]

Abstract

Synthesis and Crystal Structures of the Phosphaneimine Complexes [Cu(μ‐HNPEt3)]4(O3S–CF3)4 and [Pt2Me6(μ‐I)2(μ‐HNPMe3)] The title compounds have been prepared by the reaction of copper(I)triflate with [NiBr(NPEt3)]4 in CH2Cl2 suspension in the presence of water, and by the reaction of [PtMe3I]4 with Me3SiNPMe3 in boiling toluene in the presence of cesium fluoride, respectively. According to the crystal structure determinations the cation of the copper complex forms tetrameric units [Cu(HNPEt3)]44+ with S4 symmetry with Cu–N bond lengths of 191.6 and 192.1 pm. In the platinum complex the platinum atoms are linked by two μ‐I bridging atoms as well as by the μ‐N atom of the HNPMe3 ligand with Pt–N bond lengths of 228.1 and 229.5 pm.

Why are the {Cu4N4} rings in copper(i) phosphinimide clusters [Cu{μ-NPR3}]4(R = NMe3or Ph) planar?

“…The only structurally determined {Cu 4 N 4 } system from copper and iminophosphorane prior to our work is the tetracation [Cu 4 (NHPEt 3 ) 4 ] 4+ which is found in the saddled form. 8 The simpler model system [Cu 4 (NHPH 3 ) 4 ] 4+ was looked at computationally to establish whether the saddled form can be attributed to the steric bulk of the ethyl groups or not. There are four possible conformers based on the positions of the PH 3 and H at the nitrogensthree based on conformers A-C were looked at (see Fig.…”

A new tetranuclear copper(I) complex based on allyl(5-phenyl-1,3,4-thiadiazol-2-yl)azanide ligand: Synthesis and structural characterization

“…2). The last distance value is within the sum of the Van der Waals radii generally accepted for copper (r vdW (Cu) 1.4 Å) [37] and is quite comparable with Cu(I)Á Á ÁCu(I) distance range 2.71-2.75 Å in copper(I) benzoate [6], and is slightly elongated in comparison with corresponding contacts 2.58 and 2.60 Å in [Cu 4 (1,3-Ph 2 N 3 ) 4 ] (1,3-Ph 2 N 3 -1,3-diphenyltriazenide) [14] or 2.64 Å in [Cu(HNPEt 3 )] 4 (CF 3 SO 3 ) 4 [38]. It is worth noting that all Cu(I)Á Á ÁCu(I) distances mentioned above are much smaller than the sum (4.76 Å) of r vdW (Cu) (2.38 Å) resulted from the nearest widely analyzed distribution map for intermolecular contacts between the copper and the oxygen [39].…”

Syntheses and Characterization of Polyimidosulfate Complexes

“…This type of copper-nitrogen cycle is literature known. In 1998 and 2000, Dehnicke et al [85] and Fenske et al [86] published similar cycles, in which a copper(I) atom is coordinated by nitrogen atoms, wherein one nitrogen atom is protonated (Figure 3.2).…”

“…[Cu(NHPEt3)]4, [85] , middle: the dimer [Cu(NHtBu)]8, [86] , right: [Cu(N(SnMe3)2)]4. [86] Compound 2 is nearly equal in bond lengths and angles to these published complexes.…”

“…The Cu-Cu-Cu and the Cu-N-Cu angles in these four compounds are nearly right angles, whereby the N-Cu-N angle becomes almost 180°. [85] [Cu(NHtBu)]8, [86] [Cu(N(SnMe3)2)]4. [86] 3 The difference to the synthesis of compound 2 was the copper chloride being newly purchased and toluene instead of THF being used in the first step of the reaction.…”