259267-54-4Relevant academic research and scientific papers
Synthesis and structure of a series of new haloaryl imido complexes of molybdenum
Rufanov, Konstantin A.,Zarubin, Dmitry N.,Ustynyuk, Nikolai A.,Gourevitch, Dmitry N.,Sundermeyer, J?rg,Churakov, Andrei V.,Howard, Judith A.K.
, p. 379 - 385 (2008/10/08)
The synthesis of a series of mono- and bis-haloarylimido molybdenum(VI) complexes is described. Two methods of introducing the electron poor imido functionality are employed, first the condensation of substituted anilines with Na2MoO4 in the presence of Me3SiCl/NEt3, secondly the sulfinyl amine metathesis with [Mo(O)2Cl2(dme)] (1). The latter method works even in cases, when the first one does not work. Crystal structures of three complexes [Mo(NC6F5)(O)Cl2(dme)] (2a), [Mo(N-2.6-Cl2C6H3)2Cl 2(dme)] (3b) and [Mo(N-2.4,6-Br3C6H2)2Cl 2(dme)] (4) are reported. The unusually small Mo-N-C(Ar) angle of 149.1(5)° has been found in the structure of 4.
Bent vs. linear imido ligation at the octahedral molybdenum(VI) dithiocarbamate stabilised centre
Barrie, Patrick,Coffey, Therese A.,Forster, Glyn D.,Hogarth, Graeme
, p. 4519 - 4528 (2007/10/03)
Molybdenum(VI) bis(imido) complexes [Mo(NR)2(S2CNEt2)2] 3a-3p have been prepared via two synthetic routes and their structures investigated. Thermolysis of [MoO2(S2CNEt2)2] 1 with 2,6-disubstituted aryl isocyanates affords air-stable bis(imido) complexes 3i-3m in high yields after column chromatography, a route which fails for sterically less demanding isocyanates. A more general preparation involves room temperature addition of two equivalents of [S2CNEt2]- to the labile bis(imido) complexes [Mo(NR)2Cl2(dme)] 2a-2p (dme = 1,2-dimethoxyethane) to afford 3a-3p in high yields. In this manner related complexes [Mo(NR)2(S2CNMe2)2] 4 (R = Ph or But) and [Mo(NPh)2(S2PPh2)2] 5a have also been prepared. Structural and spectroscopic studies have been carried out in order to determine the degree of bending of the imido ligands. Six complexes have been characterised by X-ray crystallography. In all cases one of the imido ligands is linear (Mo-N-C ≥ 160°), while the angle at the second is dependent upon the nature of R and ranges from 180 to 139°. Solid-state 13C CPMAS spectroscopy reveals that the difference in bond angles at the two nitrogen centres (Δ°) correlates closely with the difference in chemical shifts of the ipso-carbon atoms (Δδ). This then has been used to probe the relative bond angles at nitrogen for non-crystallographically characterised complexes. In solution even at low temperatures both imido ligands are equivalent indicating a rapid interconversion between linear and bent bonding modes. The Royal Society of Chemistry 1999.
