Alkaline-earth metals, carbene complexes

It is also possible to isolate bis(carbene) complexes involving the heavier alkaline earth metals. Thus, the reaction of two equivalents of 4 (R = Me or (Bu, R = H) with calcium, strontium and barium bis(trimethylsilyl)amides [M N(SiMe3)2 2(thf)2] (M = Ca, Sr, Ba) resulted in the displacement of two thf molecules to afford the corresponding biscarbene species, 19 (19). The solubilities and stabilities of these complexes were found to decrease from calcium to barium. 

In 2001, Schumann and co-workers reported a similar set of metallocene complexes with l,3-di- o-propyl-4,5-dimethylimidazoly-2-ylidene.22 X-ray crystallography and NMR studies confirmed a similar trend between metal-carbene bond strength and alkaline earth metal as that found by Arduengo and co-workers. Additionally they showed that as the steric bulk of the cyclopentadienyl ligand increases the metal-carbene bond distance is elongated. 

Carbene complexes of alkaline earth metal amides and metallocenes have also been reported. Reaction of calcium, strontium, and barium bis(trimethylsilyl)amides [M(N(SiMe3)2 2(thf)2] (M = Ca, Sr, Ba) with two equivalents... 

The synthesis of sodium complexes 34 and 35, in which two different metals were added in situ to IPr, is essentially identical to a protocol recently reported by the Hill group. As was done with 34 and 35, Hill treated two equivalents of IPr with one equivalent each of an alkali and an alkaline earth metal salt and obtained mixed Group 1/Group 2 carbene complexes (50, Scheme 5.7). ... 

Barret and Hill have extensively studied the reactivity and catalytic activity of NHC-supported Group 2 amido complexes. Similar to several reports with the alkali metals, tricoordinate NHC-alkaline earth metal complexes 58 could be formed directly from the corresponding conjugate acid by addition of a metal amide salt (Scheme 5.8). Whereas carbene-Li complexes were found to be excellent carbene transfer reagents, 58 could function as a stable carbene equivalent. Indeed, in the presence of Lewis base donors such as triphenylphosphine oxide or protic substrates such as 2-methoxyethylamine, liberation of the free carbene was observed by and NMR. While the authors did not attempt to isolate this free carbene or investigate any additional reactivity, they claimed that the carbene was dissociated under catalyt-ically relevant conditions. 

In 1998, the same group reported the synthesis of magnesium metallocene NHC complexes, in addition to metallocene NHC complexes of other group 2 elements.21 The adducts show an interesting trend in the nature of the metal-carbene bonds which increase as metal radii increase. The trends are reflected in both the solid state structures (metal-carbene bond length increases) and the NMR spectra (downfield shift of C2) of the adducts (Table 1). In addition to mono-NHC complexes, the heavier alkaline earth elements (Sr and Ba) are capable of forming stable bis-NHC adducts. 

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