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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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Supplementary files

Article information


Submitted
16 Mar 2011
Accepted
12 Apr 2011
First published
24 May 2011

Dalton Trans., 2011,40, 6565-6574
Article type
Paper

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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