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Synthesis and structural characterization of bis and tris(2-mercapto-1-methylbenzimidazolyl)hydroborato complexes: benzannulation promotes κ³-coordination.
| Content Provider | Semantic Scholar |
|---|---|
| Author | Alharbi, Ahmed. M. Rong, Yi Parkin, Gerard |
| Copyright Year | 2013 |
| Abstract | The benzannulated bis and tris(mercaptoimidazolyl)borohydride compounds, [BmMeBenz]Na and [TmMeBenz]Na, have been synthesized via the reactions of NaBH4 with two and three equivalents of 1-methyl-1,3-dihydro-2H-benzimidazole-2-thione, respectively. X-ray diffraction studies on the THF adducts, {μ-[BmMeBenz]Na(THF)₂}₂ and {[TmMeBenz]Na}₂(μ-THF)₃, indicate that both compounds are dinuclear but differ according to the nature of the bridging ligand. Specifically, {μ-[BmMeBenz]Na(THF)₂}₂ possesses bridging [BmMeBenz] ligands and terminal THF ligands, while {[TmMeBenz]Na}₂(μ-THF)₃ possesses terminal [TmMeBenz] ligands and bridging THF ligands. The tris(mercaptoimidazolyl)borohydride ligand of {[TmMeBenz]Na}₂(μ-THF)₃ coordinates in a κ³-manner, which is in marked contrast to the κ²-, κ¹- and κ⁰-modes that have been reported for various [TmMe]Na derivatives. Density functional theory (DFT) geometry optimization calculations of the anions [TmMeBenz]⁻ and [TmMe]⁻ in the gas phase indicate that the conformation required for κ³-S₃ coordination, i.e. one in which the three sulfur donors point away from the B-H group, is relatively more stable for [TmMeBenz]⁻ than for [TmMe]⁻, and thus provides a rationalization for the observation that benzannulation enables κ³-coordination of tris(mercaptoimidazolyl)borohydride ligand in {[TmMeBenz]Na}₂(μ-THF)₃. Furthermore, comparison of the molecular structure and IR spectroscopic properties of [TmMeBenz]Re(CO)₃ with those of [TmMe]Re(CO)₃ indicates that benzannulation reduces the electron donating properties of the ligand, but has little effect on its steric properties. {μ-[BmMeBenz]Na(THF)₂}₂ and {[TmMeBenz]Na}₂(μ-THF)₃ react with [Me₃PCuCl]₄ to give [BmMeBenz]CuPMe₃ and [TmMeBenz]CuPMe₃, the first pair of structurally related bis and tris(mercaptoimidazolyl)hydroborato copper(I) compounds. |
| File Format | PDF HTM / HTML |
| DOI | 10.1039/c3dt51092a |
| PubMed reference number | 23801309 |
| Journal | Medline |
| Volume Number | 42 |
| Issue Number | 31 |
| Alternate Webpage(s) | http://www.rsc.org/suppdata/dt/c3/c3dt51092a/c3dt51092a.pdf |
| Alternate Webpage(s) | https://doi.org/10.1039/c3dt51092a |
| Journal | Dalton transactions |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |
