74255-77-9Relevant articles and documents
New phosphoraneiminato complexes of molybdenum and tungsten. Crystal structures of [(μ-S2N2){MoCl4(NPPh3)} 2], [Mo(NPPh3)4] [BF4]2, [W(S)2(NPPh3)2], and [Ph3PNH2]+[SCN]-
Dietrich, Armin,Neumueller, Bernhard,Dehnicke, Kurt
, p. 1837 - 1844 (2008/10/08)
The binuclear molybdenum(V)phosphoraneiminato complex [(μ-S2N2){MoVCl4(NPPh 3)}2] (1) has been prepared by the reaction of the chlorothionitreno complex [MoVICl4(NSCl)]2 with Me3SiNPPh3 in dichloromethane forming green crystals. The temperature dependent magnetic susceptibility in the range of 2-30 K shows ideal behaviour according to the Curie law with a magnetic moment of 1.60 B.M. According to the crystal structure determination 1 forms centrosymmetric molecules in which the molybdenum atoms are connected by the nitrogen atoms of the S2N2 molecule. In trans-position to it the nitrogen atoms of the phosphoraneiminato groups (NPPh3) are coordinated with Mo-N bond lengths of 171(1) pm. The tetrakis(phosphoraneiminato) complex [Mo(NPPh3)4]-[BF4]2 (2) has been obtained as colourless crystal needles by the reaction of MoN(NPPh3)3 with boron trifluoride etherate in toluene solution. In the dication the molybdenum atom is tetrahedrally coordinated by the nitrogen atoms of the (NPPh3-) groups with Mo-N bond lengths of 179,8-181,0(3) pm. The dithio-bis(phosphoraneiminato) tungsten complex [W(S)2(NPPH3)2] (3) is formed as yellow crystals as well as [Ph3PNH2]+[SCN]- (4) from the reaction of WN(NPPh3)3 with carbon disulfide in tetrahydrofurane in the presence of traces of water. 3 has a monomeric molecular structure with tetrahedrally coordinated tungsten atom with bond lengths W-S of 214.5(5) pm and W-N of 179(1) pm. In the structure of 4 the thiocyanate ions are associated by hydrogen bonds of the NH2 group of the [Ph3PNH2]+ ion to give a zigzag chain. 1: Space group Pbca, Z = 4, lattice constants at -80°C: a = 1647.9(3), b = 1460.8(2), c = 1810.4(4) pm; R1 = 0.0981. 2: Space group P1, Z = 2, lattice constants at -80°C: a = 1162.5(1), b = 1238.0(1), c = 2346.2(2) pm; α = 103.14(1)°, β = 90.13(1)°, γ = 97.66(1)°; R1 = 0.0423. 3: Space group Fdd2, Z = 8, lattice constants at -80°C: a = 3310.1(4), b = 2059.7(2), c = 966,7(1) pm; R1 = 0.0696. 4: Space group P212121, Z = 4, lattice constants at -80°C: a = 1118.4(1), b = 1206.7(1), c = 1279.9(1) pm; R1 = 0.0311.
