Syntheses, molecular structures, and self-assemblies of SFe₃, S₂Fe₃, S₃Fe₅, SeFe₃, and Se₂Fe₃ clusters with chelating diaminocarbenes

Abstract

The reactions of substituted thioureas and selenoureas with iron carbonyls have been systematically investigated, and five types of SFe₃, S₂Fe₃, S₃Fe₅, SeFe₃, and Se₂Fe₃ clusters with chelating diaminocarbenes have been synthesized and characterized by X-ray crystallography. The reactions of C₃H₅NHC(=S)NHAr with Fe₃(CO)₁₂ afford (μ₃-S)Fe₃(CO)₇(μ-CO)(κ³C,C,C-C₃H₅NHCNHAr) (1, Ar = Ph; 2, Ar = 4-H₂NC₆H₄). In contrast, the reactions of (2-C₅H₄N)NHC(=S)NHN=CHAr with Fe₂(CO)₉ form (μ₃-S)₂Fe₃(CO)₇(κ²N,C-(2-C₅H₄N)NHCNHN=CHAr) (3, Ar = Ph; 4, Ar = 4-CH₃C₆H₄). Likewise, reactions of GNHC(=S)NHC(=O)Ph with Fe₃(CO)₁₂ provide (μ₃-S)₂Fe₃(CO)₇(κ²N,C-GNHCNHC(=O)Ph) (5, G = 2-C₅H₄N; 6, G = 2-C₄H₃N₂) as well as Fe₃(CO)₈(μ-CO)₂(κ²N,C-(2-C₄H₃N₂)NHCNHC(=O)Ph). The reaction of (2-C₅H₄N)NHC(=S)NH₂ with Fe₃(CO)₁₂ gives (μ₃-S)₂Fe₃(CO)₇(κ²N,C-(2-C₅H₄N)NHCNH₂) (7). The reactions of GNHC(=S)NHPh with Fe₃(CO)₁₂ produce (μ₃-S)₂Fe₃(CO)₇(κ²N,C-GNHCNHPh) (8, G = 2-C₅H₄N; 9, G = 2-C₄H₃N₂). Analogously, (2-C₅H₄N)NHC(=S)NH(2-CH₃C₆H₄) offers (μ₃-S)₂Fe₃(CO)₇(κ²N,C-(2-C₅H₄N)NHCNH(2-CH₃C₆H₄)) (10). However, (2-C₅H₄N)NHC(=S)NH(2-CH₃OC₆H₄) generates (μ₃-S)₂(μ₄-S)Fe₅(CO)₁₀(μ-CO)₂(κ²N,C-(2-C₅H₄N)NHCNH(2-CH₃OC₆H₄)) (11). Furthermore, the reactions of (2-C₅H₄N)NHC(=S)NHR with Fe₃(CO)₁₂ form (μ₃-S)₂(μ₄-S)Fe₅(CO)₁₀(μ-CO)₂(κ²N,C-(2-C₅H₄N)NHCNHR) (12, R = 2-H₂NC₆H₄; 13, R = 4-H₂NC₆H₄; 14, R = 2-C₅H₄N). Surprisingly, the reaction of (2-C₅H₄N)NHC(=S)NHC₃H₅ with Fe₃(CO)₁₂ leads to (μ₃-S)₂(μ₄-S)Fe₅(CO)₁₀(μ-CO)₂(κ²N,C-(2-C₅H₄N)NHCNHC₃H₅) (15). The reaction of C₃H₅NHC(=Se)NHPh with Fe₃(CO)₁₂ affords (μ₃-Se)Fe₃(CO)₇(μ-CO)(κ³C,C,C-C₃H₅NHCNHPh) (16) as well as [(κ²N,C-PhNCNHC₃H₅)Fe₂(CO)₆(μ₄-Se)Fe₂(CO)₆]₂(μ₄-Se). As with (2-C₄H₃N₂)NHC(=S)NHPh, (2-C₄H₃N₂)NHC(=Se)NHPh offers (μ₃-Se)₂Fe₃(CO)₇(κ²N,C-(2-C₄H₃N₂)NHCNHPh) (17). Unlike (2-C₅H₄N)NHC(=S)NH(2-CH₃OC₆H₄), (2-C₅H₄N)NHC(=Se)NH(2-CH₃OC₆H₄) yields (μ₃-Se)₂Fe₃(CO)₇(κ²N,C-(2-C₅H₄N)NHCNH(2-CH₃OC₆H₄)) (18). By virtue of N–HN, N–HO, and C–HO intermolecular hydrogen bonds along with other non-covalent interactions, these new organometallic clusters exhibit interesting supramolecular structures.

Keywords:

• Fe/S cluster
• Fe/Se cluster
• Diaminocarbene
• Thiourea
• Selenourea

Disclosure statement

The authors declare no competing financial interest.

Supplementary data

Supplementary data related to this article can be accessed online at http://dx.doi.org/10.1080/00958972.2015.1079312.

Additional information

Funding

The authors are grateful to the Mao Zedong Foundation of China, Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), Natural Science Foundation of China [grant number 20572091], and Natural Science Foundation of Jiangsu Province [grant number 05KJB150151] for financial support of this work.