The Molecular Structure of a Tricyclic Complex, [SFe(CO)₃]₂

Synthesis, Structure, and Spectroelectrochemical Investigation of Novel Ternary Co/S(Se)/Sn Clusters Derived from Binary Cobalt Stannanediyl Complexes

“…The SÀS bond length is 3.28 . This is well out of the range of E À E bond lengths found in tetrahedral transition metal clusters ([Fe 2 (m-E 2 )(CO 6 )] [14] ) of the bis-chalcogeno bridged Hieber ± Gruber-type A (E S, 2.86 ; [15] E Se, 2.293(2) [16] ), in which EÀE bonding of the bridging chalcogenes has been established in fundamental work by Dahl and co-workers. [15,16] These short E À E bond lengths suggest a significantly enhanced nucleophilicity for the EÀE bridge.…”

“…This is well out of the range of E À E bond lengths found in tetrahedral transition metal clusters ([Fe 2 (m-E 2 )(CO 6 )] [14] ) of the bis-chalcogeno bridged Hieber ± Gruber-type A (E S, 2.86 ; [15] E Se, 2.293(2) [16] ), in which EÀE bonding of the bridging chalcogenes has been established in fundamental work by Dahl and co-workers. [15,16] These short E À E bond lengths suggest a significantly enhanced nucleophilicity for the EÀE bridge. [15±17] Owing to the long SÀS atomic bond length in 8 relative to that in [Fe 2 (m-S 2 )(CO 6 )], [14] a lower basicity is expected, and hence a corresponding reactivity pattern as was observed for [Fe 2 (m-S 2 )(CO 6 )] [16,17] is not to be expected for 8.…”

“…In all structures, the two Co atoms and the Sn atom form a triangle that is bridged by two capping m 3 -E atoms ( Figure 4 and Figure 5). Presumably, from the steric strain, the CoÀCo bond lengths in 9 and 16 are significantly elongated relative to those in 15; this reflects the sterically encumbered situation imposed on the cluster geometry by the Me 5 Cp (16,9) vs. Cp ligands (15). The basal {(Cp)Co} 2 units contain a CoÀCo bond while the apical SnR 2 fragment is tetrahedrally coordinated with two of these coordination sites occupied by bridging chalcogen atoms.…”

1,3-Dipolar cycloaddition to the FeSC fragment 20. Preparation and properties of carbonyliron complexes of di-thiooxamide. Reactivity of the mononuclear (di-thiooxamide)Fe(CO)3 towards dimethyl acetylenedicarboxylate

“…Complexes 8 are further characterised spectroscopically and by elemental analyses. Reaction of Fe 2 (CO) 9 with di-thiooxamide (e) does not result in a detectable concentration of Fe(CO) 3 -(DTO) (7e); instead, the known complexes Fe 3 (CO) 9 S 2 (14) [37] and Fe 2 (CO) 6 S 2 (15) [56] are formed in low yield.…”

Note

“…Chromatography was carried out on columns of 160 ± 200 silica gel mesh. Co 2 (CO) 8 [9] and dipropargyl terephthalate [10] were prepared by literature methods using slight modi®cations. The NMR measurements were made with a Bruker AM400 M Hz spectrometer.…”