First examples of homogeneous hydrogenolysis of thiophene to 1-butanethiolate and ethylthioketene ligands: Synthesis and reactivity of ([eta][sup 4]-C[sub 4]H[sub 5]S)ReH[sub 2](PPh[sub 3])[sub 2]

Journal Article · Wed Dec 30 04:00:00 EST 1992 · Journal of the American Chemical Society; (United States)

DOI:https://doi.org/10.1021/ja00053a013· OSTI ID:6305007

Rosini, G P; Jones, W D ^[1]

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1. Univ. of Rochester, NY (United States)

The reaction of ReH[sub 7](PPh[sub 3])[sub 2] with excess thiophene in the presence of the hydrogen acceptor 3,3-dimethyl-1-butene results in the formation of a new organometallic complex which has been identified as the thioallyl complex ([eta][sup 4]-C[sub 4]H[sub 5]S)ReH[sub 2](PPh[sub 3])[sub 2] (1). The thermolysis of a solution of 1 at 60[degrees]C with excess trimethylphosphine results in the formation of free tetrahydrothiophene and the new cyclometalated organometallic complex [ovr Re(PMe[sub 3])[sub 4](PPh[sub 2]C][sub 6]H[sub 4]) (2). Photolysis of a solution of 1 with excess trimethylphospine proceeds differently, yielding a mixture of four new organometallic complexes, all of which contain a C-S-cleaved 1-butene-1-thiolate ligand. Two of the complexes contain an S-bound ethenethiolate ligand and exist as cis and trans isomers of Re(SCH[double bond]CHEt)(PMe[sub 3])[sub 5] (3a,b), while the other two complexes contain an [eta][sup 3]-allyl-bound ethenethiolate ligand and exist as cis and trans isomers of Re([eta][sup 3]-SCH[double bond]CHEt)(PMe[sub 3])[sub 4] (4a,b). In both complexes the cis is the more thermodynamically stable isomer. The cis complex 3a is seen to isomerize to the trans 3b photochemically (cis:trans = 1.6:1), while thermally the trans isomerizes almost totally to the cis (cis:trans = 10:1 after several days). In the presence of a large excess of PMe[sub 3], only complexes 3a,b are seen, whereas removal of the free phosphine from solution gives only complexes 4a,b. 23 refs., 6 figs., 3 tabs.

• OSTI ID: 6305007
• Journal Information: Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 114:27; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COMPLEXES
CRYSTAL LATTICES
CRYSTAL STRUCTURE
DECOMPOSITION
ELEMENTS
HETEROCYCLIC COMPOUNDS
HYDRIDES
HYDROGEN
HYDROGEN COMPOUNDS
HYDROGENATION
ISOMERS
MONOCLINIC LATTICES
NONMETALS
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
ORGANOMETALLIC COMPOUNDS
PHOSPHINES
PHOSPHORUS COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
REFRACTORY METAL COMPOUNDS
RHENIUM COMPLEXES
RHENIUM COMPOUNDS
RHENIUM HYDRIDES
SULFUR COMPOUNDS
SYNTHESIS
THIOPHENE
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS