Synthesis, reactivity, and variable-temperature NMR studies of transition-metal complexes containing the 2,3-dihydrothiophene ligand

Journal Article · Wed Jul 01 00:00:00 EDT 1987 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00260a030· OSTI ID:6295511

Sauer, N N; Angelici, R J

The transition-metal complexes W(CO)5(2,3-DHT) (1), (Re(CO)5(2,3-DHT))SO3CF3 (3), PdCl2(2,3-DHT)2 (4), and Ru(CO)3Cl2(2,3-DHT) (5) containing S-bound 2,3-dihydrothiophene (2.3-DHT), a proposed intermediate in thiophene hydrodesulfurization, have been prepared and characterized. Variable-temperature H NMR studies of complexes 1, 3, and 5 establish that the barrier to inversion of the coordinated sulfur increases with the oxidation state of the metal: W(O) < Re(I) < Ru(II). In the series of W(CO)5(L) complexes, where L = 2,3-DHT, 2,5-DHT, and tetrahydrothiophene (THT), the inversion barriers decrease in the order 2,3-DHT (48.5 kJ/mol) > 2,5-DHT (45.6) > THT (43.9), which is also the order of decreasing ring strain in the sulfur ligands. Thus, the less strained the ligand, the more easily it achieves the planar transition state required for inversion. 30 references, 3 figures.

• Research Organization: Iowa State Univ., Ames
• DOE Contract Number: W-7405-ENG-82
• OSTI ID: 6295511
• Journal Information: Inorg. Chem.; (United States), Vol. 26:13
• Country of Publication: United States
• Language: English

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37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
POLYCYCLIC SULFUR HETEROCYCLES
CHEMICAL REACTIONS
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SYNTHESIS
TRANSITION ELEMENT COMPLEXES
TEMPERATURE EFFECTS
COMPLEXES
HETEROCYCLIC COMPOUNDS
MAGNETIC RESONANCE
ORGANIC COMPOUNDS
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400201* - Chemical &amp; Physicochemical Properties