Reaction of H2FeRu3(CO)13 with Alkynes. Preparation and Characterization of Isomeric FeRu3(CO)12(RC≡CR') Clusters. A Definitive Structural Characterization of the µ4- η2- Bonding Mode for Substituted Alkynes

Inorganic Chemistry

Volumn 20, Issue 10, 1981, Pages 3230-3237

  Fox, Joseph R ^a   Gladfelter, Wayne L ^a   Geoffroy, Gregory L ^a   Tavanaiepour, Iraq ^b   Abdel Mequid, Sherin ^b   Day, Victor W ^b  

^a PENNSYLVANIA STATE UNIVERSITY   (United States)

^b UNIVERSITY OF NEBRASKA LINCOLN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000873913     PISSN: 00201669     EISSN: 1520510X     Source Type: Journal    
DOI: 10.1021/ic50224a019     Document Type: Article

References (45)

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25. Computer programs employed in this study with an IBM 360-65 or 370-158 computer: magtape, scalup, and SCTFT4, data reduction programs by V.W. Day; fordap, Fourier and Patterson synthesis program; fame, a Wilson plot and normalized structure factor program by R. Dewar and A. Stone; multan, direct-methods program by P. Main, M.M. Woolfson, and G. Germain; orflse, full-matrix leastsquares refinement program, a highly modified version of Busing, Martin, and Levy’s original orfls; orffe, bond lengths and angles with standard deviations by Busing, Martin, and Levy; ortepz, thermal ellipsoid plotting program by C.K. Johnson
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29. The percent isomerization in each case was estimated from the relative intensities of the IR bands of each isomer.
30. H2FeRu3(CO)13 was heated in a refluxing hexane solution that was continuously purged with C2H2. Mass spectral evidence suggested the formation of a small amount of FeRu4(CO)15C (parent ion mje 896; stepwise loss of 15 CO ligands) and FeRu2(CO)10(C2H2) (parent ion m/e 566; stepwise loss of 10 CO ligands), but these could not be isolated in sufficient quantities to characterize,
31. Reaction between r-BuC= C-t-Bu and H2FeRu3(CO)l3 in refluxing hexane gave at least three products, which were not fully characterized but definitely were shown not to be FeRu3C2 clusters by infrared and mass spectral analyses,
32. When H2FeRu3(CO)13 was treated with C6H5CsCH in refluxing hexane, the solution darkened considerably. Evaporation of solvent gave a brown tar, from which no characterzable compounds could be obtained.
33. Wade, K., Adv. Inorg. Chem. Radiochem. 1976, 18, 1.
34. Fe(8) + 3Ru(24) + 2C(8) + 12CO(24) + 2C6H5(2) = 66 valence electrons; 52 electrons required for ligand bonding and nonbonding orbitals [Fe(l2) + 3Ru(36) + 2C(4)]; 66-52 = 14 = 2n + 2 for = 6.
35. Stuntz, G.F.; Shapley, J.R.; Pierpont, C.G. Inorg. Chem. 1978, 17, 2596.
36. The first number in parentheses following an average value for a bond length or angle is the root-mean-square estimated standard deviation of an individual datum. The second and third numbers, when given, are the average and maximum deviations from the averaged value, respectively; the fourth number is the number of individual values included in the average.
37. Cotton, F.A.; Day, V.W.; Hazen, E.E., Jr.; Larsen, S.J. Am. Chem. Soc. 1973, 95, 4834.
38. Cotton, F.A.; Day, V.W.; Hazen, E.E., Jr.; Larsen, S.; Wong, S.T.K. J. Am. Chem. Soc. 1974, 96, 4471.
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40. Churchill, M.R. Inorg. Chem. 1973, 12, 1213. 37) In the original synthesis, the yield of 2a was greater than that of 2b. This reaction however was run at 83 °C, as opposed to 70 °C for the other alkynes. We believe these conditions accelerated the isomerization of 2b initially formed from 2a. For the phenylmethylacetylene clusters, the yield of the 3b/3c mixture was greater than that of 3a.
41. Wang, Y.; Coppens, P. Inorg. Chem. 1976, 15, 1122.
42. Thomas, M.G.; Muetterties, E.L.; Dav, R.O.; Day, V.W. J. Am. Chem. Soc. 1976, 98, 4645.
43. Day, V.W.; Abdel-Mequid, S.S.; Dabestani, S.; Thomas, M.G.; Pretzer, W.R.; Muetterties, E.L. J. Am. Chem. Soc. 1976, 98, 8289.
44. Muetterties, E.L. Bull. Soc. Chim. Belg. 1976, 85, 451.
45. “Tables of Interatomic Distances and Configurations in Molecules and Ions”; The Chemical Society: London; Vol. 11, p M12