Dimerization of pentanuclear clusters [Fe3Q(AsMe)(CO)9] (Q = Se, Te) as a conversion pathway to novel cubane-like aggregates

Abstract

The first examples of carbonyl heterocubane-type clusters, [Fe 4 (m 3 -Q) 2 (m 3 -AsMe) 2 (CO) 12 ] (2, Q = Se (a), Te (b)), which simultaneously contain elements of group 15 and 16, were obtained by thermolysis of [Fe 3 (m 3 -Q)(m 3 -AsMe)(CO) 9 ] (1) in acetonitrile. The clusters 2 possess a cubic Fe 4 Q 2 As 2 core with alternating Fe and Q/As atoms. The coordination environment of the Fe atoms is close to octahedral, and those of Q or As atoms are tetrahedral, which determines the distorted cubic cluster core geometry.

High‐Spin and Reactive Fe13 Cluster with Exposed Metal Sites

“…[36] The FeÀ Fe distances are between 2.395(2) and 2.771(2) Å (Table S1), within the range of metal-metal bonds for molecular Fe complexes. [37,38] The WÀ S distances match the parameters observed for reduced Tp*WFe 3 S 3 clusters supported by N-heterocyclic carbene ligands at Fe. [35] The FeÀ S bonds show a significant lengthening relative to the precursor, consistent with reduction at Fe.…”

“…Tp* 4 W 4 Fe 13 S 12 consists of four Tp*WS 3 units tetrahedrally arranged (Figure 1D) around a pseudo‐icosahedral Fe 12 core with an additional Fe atom bound in the center [36] . The Fe−Fe distances are between 2.395(2) and 2.771(2) Å (Table S1), within the range of metal‐metal bonds for molecular Fe complexes [37,38] . The W−S distances match the parameters observed for reduced Tp*WFe 3 S 3 clusters supported by N‐heterocyclic carbene ligands at Fe [35] .…”

New Main-Group-Element-Rich nido-Octahedral Cluster System: Synthesis and Characterization of [Et4N][Fe2(CO)6(μ3-As){μ3-EFe(CO)4}2]

“…The related M 3 E 2 nido- octahedral compounds have been known for some time, − and the compounds reported here may be viewed as an isolobal replacement of Fe­(CO) 3 – by P or As. [Et 4 N]­[ II ] and [Et 4 N]­[ III ] are electron precise, and the core electron count of each is consistent with that predicted by the Wade–Mingos rules for a nido- octahedron with seven skeletal electron pairs distributed across five vertices …”

“…The related M 3 E 2 nido-octahedral compounds have been known for some time, 16 6 (μ 3 -E)}{μ 3 -EFe(CO) 4 } 2 ] − compounds possible with an Fe 2 E 3−x E′ x core, namely, As 3 , P 3 , As 2 P (isomers A and B), and AsP 2 (isomers A and B). skeletal electron pairs distributed across five vertices.…”