Synthesis and x-ray crystallographic structural determination of the acetylene complex (η5?C5H5)2W2(CO)4(C2H2) |
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| Authors: | David S Ginley C Randolph Bock Mark S Wrighton Beda Fischer Donald L Tipton Robert Bau |
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| Institution: | Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 U.S.A.;Department of Chemistry, University of Southern California, Los Angeles, California 90007 U.S.A. |
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| Abstract: | Reaction of photogenerated (η5?C5H5)2W2(CO)4 with acetylene at 25°C yields a complex of the formula (η5-C5H5)2W2(CO)4(C2H2). The crystal structure of the complex shows it to have a tetrahedrane-like W2C2 core. The C—C bond distance of the C2H2 unit is 1.33 Å which is close to that of ethylene, considerably longer than the 1.20 Å for acetylenes. The W—W distance is 2.987 Å which is ～0.25 Å shorter than the W—W distance in (η5-C5H5)2W2(CO)6 but longer than that expected for (η5-C5H5)2W2(CO)4. By analogy to the parent (η5-C5H5)2M2(CO)6 species, the near-UV absorption in (η5-C5H5)2M2(CO)4(C2H2) is assigned to a σb → σ* transition. Owing to the shorter M—M bond in the C2H2 adducts, the σb → σ* absorption is at higher energy than in the (η5-C5H5)2M2(CO)6 complexes. |
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