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Issue 24, 2011
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Hybrid dibismuthines and distibines as ligands towards transition metal carbonyls

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Abstract

The hybrid dibismuthines O(CH2CH2BiPh2)2 and MeN(CH2-2-C6H4BiPh2)2 react with [M(CO)5(thf)] (M = Cr or W) to form [{M(CO)5}2{O(CH2CH2BiPh2)2}] and [{Cr(CO)5}2{MeN(CH2-2-C6H4BiPh2)2}] containing bridging bidentate (Bi2) coordination. The unsymmetrical tertiary bismuthine complexes [M(CO)5{BiPh2(o-C6H4OMe)}] are also described. Depending upon the molar ratio, the hybrid distibines O(CH2CH2SbMe2)2 and MeN(CH2-2-C6H4SbMe2)2 react with [M(CO)5(thf)] to give the pentacarbonyl complexes [{M(CO)5}2{O(CH2CH2SbMe2)2}] and [{Cr(CO)5}2{MeN(CH2-2-C6H4SbMe2)2}] or tetracarbonyls cis-[M(CO)4{O(CH2CH2SbMe2)2}] and cis-[M(CO)4{MeN(CH2-2-C6H4SbMe2)2}]. The latter can also be obtained from [Cr(CO)4(nbd)] or [W(CO)4(pip)2], and contain chelating bidentates (Sb2-coordinated) as determined crystallographically. S(CH2-2-C6H4SbMe2)2 coordinates as a tridentate (SSb2) in fac-[M(CO)3{S(CH2-2-C6H4SbMe2)2}] (M = Cr or Mo) and fac-[Mn(CO)3{S(CH2-2-C6H4SbMe2)2}][CF3SO3]. Fac-[Mn(CO)3{MeN(CH2-2-C6H4SbMe2)2}][CF3SO3] contains NSb2-coordinated ligand in the solid state, but in solution a second species, Sb2-coordinated and with a κ1-CF3SO3 replacing the coordinated amine is also evident. X-ray crystal structures were also determined for fac-[Cr(CO)3{S(CH2-2-C6H4SbMe2)2}], fac-[Mn(CO)3{S(CH2-2-C6H4SbMe2)2}][CF3SO3] and fac-[Mn(CO)3{MeN(CH2-2-C6H4SbMe2)2}] [CF3SO3]. Hypervalent N⋯Sb interactions are present in cis-[M(CO)4{MeN(CH2-2-C6H4SbMe2)2}] (M = Mo or W), but absent for M = Cr.

Graphical abstract: Hybrid dibismuthines and distibines as ligands towards transition metal carbonyls

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Publication details

The article was received on 16 Mar 2011, accepted on 12 Apr 2011 and first published on 24 May 2011


Article type: Paper
DOI: 10.1039/C1DT10447K
Citation: Dalton Trans., 2011,40, 6565-6574

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    Hybrid dibismuthines and distibines as ligands towards transition metal carbonyls

    S. L. Benjamin, W. Levason, G. Reid and M. C. Rogers, Dalton Trans., 2011, 40, 6565
    DOI: 10.1039/C1DT10447K

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