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Light‐Induced Codimerisation of Acetylene and Olefins at a Binuclear Tungsten Complex
Author(s) -
Kreiter Cornelius G.,
Kern Ulrich,
Wolmershäuser Gotthelf,
Heckmann Gert
Publication year - 1998
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199801)1998:1<127::aid-ejic127>3.0.co;2-0
Subject(s) - chemistry , acetylene , ethylene , propene , diastereomer , medicinal chemistry , yield (engineering) , olefin fiber , carbene , crystal structure , stereochemistry , crystallography , catalysis , organic chemistry , materials science , metallurgy
[W 2 (η 5 ‐C 5 H 5 ) 2 (CO) 4 (μ‐η 2:2 ‐C 2 H 2 )] ( 1 ) and ethylene ( A ) react when irradiated with UV light at 253 K predominantly to [W 2 (η 5 ‐C 5 H 5 ) 2 (CO) 3 (μ‐η 1:4 ‐C 4 H 5 )(μ‐H)] ( 3A ), [W 2 (η 5 ‐C 5 H 5 ) 2 (CO) 4 (μ‐η 1:3 ‐C 4 H 6 )] ( 4A ), and thermolabile [W 2 (η 5 ‐C 5 H 5 ) 2 (CO) 3 (η 4 ‐C 4 H 6 )] ( 5A ). Similarly, propene ( B ), 1‐butene ( C ), and ( E )‐2‐butene ( D ) yield mixtures of [W 2 (η 5 ‐C 5 H 5 ) 2 (CO) 3 (μ‐H)(μ‐η 1:4 ‐1,3‐dien‐1‐yl)] ( 3B , 3 C , 3D ), [W 2 (η 5 ‐C 5 H 5 ) 2 (CO) 4 (μ‐η 1:3 ‐C 4 H 5 R] ( 4B , 4C ), and [W 2 (η 5 ‐C 5 H 5 ) 2 (CO) 2 (μ‐η 1:2 ‐CO)(η 4 ‐1,3‐diene) ( 5B , 5 C , 5D ). With B and C also thermolabile [W 2 (η 5 ‐C 5 H 5 ) 2 (CO) 3 (μ‐η 2:2 ‐C 2 H 2 )(η 2 ‐C 2 H 3 R)] ( 2B , 2C ) are formed. A by‐product of the reaction of 1 with D is [W(η 5 ‐C 5 H 5 )(CO)(H){η 4 ‐( E )‐C 5 H 7 CH 3 }], which is generated in two diastereomeric forms ( 6 , 6 ′). In contrast, 1 yields no complexes with ( Z )‐2‐butene ( E ) which contain ligands formed from coordinated acetylene and the olefin. From the reaction mixture only trinuclear [W 3 (η 5 ‐C 5 H 5 ) 3 (CO) 5 (μ‐η 1:2 ‐C 2 H 3 )] ( 7 ) was isolated, an alicyclic complex with a W−W single and a W−W triple bond. The crystal and molecular structures of 5D and 7 were determined by X‐ray structure analysis. The constitutions of the other complexes were ascertained by IR and 1 H‐NMR spectroscopy.