Five-co-ordinate nitrosyl thiolato-complexes of molybdenum and tungsten. The preparation and X-ray crystal structures of [NHEt3][Mo(SPh)4(NO)],[PPh4][WCl(SPh)3(NO)], and [Mo(SC6H2Pri3-2,4,6)3(NH3)(NO)]
Abstract
Reaction of either [MCl3(PPh3)2(NO)](M = Mo or W) or ‘{Mo(NH2O)(H2O)x(NO)}n’ with –SR (R = Ph, C6H4Me-4, C6H4Cl-4, C6H2Me3-2,4,6, or But) in methanol gives the anionic five co-ordinate complexes [M(SR)4(NO)]–(M = Mo; R = Ph, C6H4Me-4, C6H4Cl-4, or C6H2Me3-2,4,6), [MCl(SR)3(NO)]–(M = Mo, R = But; M = W, R = Ph). Crystal data: for [NHEt3][Mo(SPh)4(-NO)], space group P21/n with a= 10.996(2), b= 16.127(4), c= 18.845(4)Å, α= 90.00, β= 105.94(1), γ= 90.00°, and Z= 4; 2 786 reflections used in structure solution, giving R= 0.0516; for [PPh4][WCl(SPh)3(NO)], space group P21/c, a= 10.809(1), b= 19.677(3),c= 19.250(3)Å, α= 90.00, β= 105.85(1), γ= 90.00°, and Z= 4;1 895 reflections giving R= 0.0375. Both anions have overall trigonal-bipyramidal geometries with apical NO groups. The reaction of the polymeric species ‘{Mo(NH2O)(H2O)x(NO)}n’ with the sterically hindered thiol 2,4,6-tri-isopropylthiophenol in refluxing methanol affords the ammine complex [Mo(SC6H2Pri3-2,4,6)3(NH3)(NO)]. Crystal data: space group P21/n with a= 10.477(3), b= 26.359(5), c= 20.1 24(4)Å, β= 87.21(1)°, and Z= 4; 1 040 reflections giving R= 0.078. The complex againhas trigonal-bipyramidal geometry with apical NO and NH3 groups. The co-ordinated ammonia ligand arises from reduction of the co-ordinated hydroylamido-group.