2014
DOI: 10.1021/ic4025102
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Ligand Dynamics of tert-Butyl Isocyanide Oxido Complexes of Molybdenum(IV)

Abstract: The six-coordinate molybdenum(IV) oxido isocyanide complex 1 [Δ,Λ-OC-6-2-3-[MoO(N(p)∩N(i))2(CN(t)Bu)]; N(p)∩N(i) = 4-tert-butylphenyl(pyrrolato-2-ylmethylene)amine] is obtained in diastereomerically pure form in the solid state, as revealed by single-crystal X-ray diffraction. In solution, this stereoisomer equilibrates with the Δ,Λ-OC-6-2-4 diastereomer 2 at ambient temperature. The stereochemistry of both isomers has been elucidated by NMR, IR, and UV/vis spectroscopy in combination with density functional t… Show more

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Cited by 14 publications
(18 citation statements)
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“…Complexes 4 and 5 cleanly reacted with molecular dioxygen, indicated by a quick color change from red-brown to orange-red, to form oxido peroxido compounds 8 and 9 in excellent yields (Scheme 5). 23 Comparing the structure of the oxido peroxido compounds 8 and 9 with previously published cis oxido peroxido complexes originating from O 2 activation, it is evident that the O,O isomeric form is the preferred conformation for such compounds in solid state. 16 Compounds 6 and 7 were virtually non-reactive toward molecular oxygen at ambient conditions.…”
Section: Resultsmentioning
confidence: 84%
“…Complexes 4 and 5 cleanly reacted with molecular dioxygen, indicated by a quick color change from red-brown to orange-red, to form oxido peroxido compounds 8 and 9 in excellent yields (Scheme 5). 23 Comparing the structure of the oxido peroxido compounds 8 and 9 with previously published cis oxido peroxido complexes originating from O 2 activation, it is evident that the O,O isomeric form is the preferred conformation for such compounds in solid state. 16 Compounds 6 and 7 were virtually non-reactive toward molecular oxygen at ambient conditions.…”
Section: Resultsmentioning
confidence: 84%
“…(7)) with the equilibrium constants K 293 = 12 × 10 −3 (E = O) and K 333 = 2 × 10 −3 (E = N t Bu), respectively [82]. The lability and volatility of the PMe 3 ligand in the oxido phosphane Mo IV complexes can be exploited to introduce other monodentate ligands at Mo IV such as isonitriles (see below) [97].…”
Section: Atom Transfer and The Problems Of Dinucleation And Substratementioning
confidence: 99%
“…by tert-butyl isonitrile, to give Mo(L 3 ) 2 (CN t Bu)O (Scheme 9, Eq. (9)) [97]. Mo(L 3 ) 2 (CN t Bu)O crystallizes as the OC-6-2-3 stereoisomer with N p trans to the oxido ligand and N i trans to the isonitrile (Fig.…”
Section: Stereochemical Aspects and Ligand Lability In Oxido Molybdenmentioning
confidence: 99%
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