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Comments on Inorganic Chemistry
A Journal of Critical Discussion of the Current Literature
Volume 17, 1995 - Issue 1
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Original Articles

Structural Lessons from Main-Group Metallocenes

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Pages 41-77 | Received 01 Sep 1994, Published online: 23 Sep 2006

References

  • Williams , R. A. , Tesh , K. F. and Hanusa , T. P. 1991 . J. Am. Chem. Soc. , 113 : 4843
  • Burkey , D. J. and Hanusa , T. P. unpublished results
  • Burkey , D. J. , Williams , R. A. and Hanusa , T. P. 1993 . Organometallics , 12 : 1331
  • Burkey , D. J. , Hanusa , T. P. and Huffman , J. C. 1994 . Adv. Mater. Opt. Electron. , 4 : 1
  • Shannon , R. D. 1976 . Acta Crystallogr. , A32 : 751
  • Jutzi , P. 1986 . Adv. Organomet. Chem. , 26 : 217
  • Omae , I. 1989 . “Organotin Chemistry” . In J. Organomet. Chem. Library , Vol. 21 , Amsterdam : Elsevier .
  • Burkey , D. J. and Hanusa , T. P. Organometallics , submitted for publication
  • Janiak , C. and Schumann , H. 1991 . Adv. Organomet. Chem. , 33 : 291
  • Williams , R. A. , Hanusa , T. P. and Huffman , J. C. 1988 . J. Chem. Soc., Chem. Commun. , : 1045
  • Williams , R. A. , Hanusa , T. P. and Huffman , J. C. 1990 . Organometallics , 9 : 1128
  • Andersen , R. A. , Blom , R. , Boncella , J. M. , Burns , C. J. and Volden , H. V. 1987 . Acta Chem. Scand. , A41 : 24
  • Anderson , R. A. , Blom , R. , Burns , C. J. and Volden , H. V. 1987 . J. Chem. Soc., Chem. Commun. , : 786
  • Panattoni , C. , Bombieri , G. and Croatto , U. 1966 . Acta Crystallogr. , 21 : 823
  • Zerger , R. and Stucky , G. 1974 . J. Organomet. Chem. , 80 : 7
  • Morley , C. P. , Jutziüger , P. , Kr , C. and Wallis , J. M. 1987 . Organometallics , 6 : 1084
  • Jutzi , P. , Schlueter , E. , Hursthouse , M. B. , Arif , A. M. and Short , R. L. 1986 . J. Organomet. Chem. , 299 : 285
  • Heeg , M. J. , Janiak , C. and Zuckerman , J. J. 1984 . J. Am. Chem. Soc. , 106 : 4259
  • Grenz , M. , Hahn , E. , Du , M. W. W. and Pickardt , J. 1984 . Angew. Chem., Int. Ed. Engl. , 96 : 61
  • Hollis , T. K. , Burdett , J. K. and Bosnich , B. 1993 . Organometallics , 12 : 3385
  • Guido , M. and Gigli , G. 1976 . J. Chem. Phys. , 65 : 1397
  • Kaupp , M. , Schleyer , P. v. R. , Dolg , M. and Stoll , H. 1992 . J. Am. Chem. Soc. , 114 : 8202
  • Blom , R. , Faegri , K. Jr. and Volden , H. V. 1990 . Organometallics , 9 : 373
  • The lack of an easily rationalizable mechanism for bending of the cyclopentadienyl rings in Group 2 metallocenes has led some to propose that the bending is an artifact of crystal packing forces or of the large amplitude bending vibrations observed in the gas phase.22 The fact that all structurally characterized Ca and Ba metallocenes are bent even when well separated in the solid state (closest contact > 3.7 Å) suggests that crystal packing forces cannot be the sole inducement for bending. Furthermore, although the objection against the gas phase data is valid, precisely the same argument could be leveled against the structures of Group 14 metallocenes (see Section l.c). We consider the present evidence for intrinsically bent Group 2 metallocenes to be convincing, although truly irrefutable data will require structure determination by other techniques, e.g., microwave spectroscopy, which would demonstrate the existence of a permanent molecular dipole moment
  • Dave , L. D. , Evans , D. F. and Wilkinson , G. 1959 . J. Chem. Soc. , : 3684
  • Although some expositions of the VB hybridization scheme place the nonbonding electrons of a linear metallocene together in a single p-orbital (e.g., Ref. 27), application of Hund's rule requires the electrons to be in separate orbitals. This consequence of the hybridization argument was pointed out by Wilkinson in his first paper on the bonding in these compounds, and was used as evidence that diamagnetic Cp2Sn was not linear.25
  • Elschenbroich , C. and Salzer , A. 1992 . Organometallics: A Concise Introduction , New York : VCH Publishers .
  • Dory , T. S. and Zuckerman , J. J. 1984 . J. Organomet. Chem. , 264 : 295
  • Baxter , S. G. , Cowley , A. H. , Lasch , J. G. , Lattman , M. , Sharum , W. P. and Stewart , C. A. 1982 . J. Am. Chem. Soc. , 104 : 4064
  • Almlof , J. , Fernholt , L. , Faegri , K. J. , Haaland , A. , Schilling , B. E. R. , Seip , R. and Taugboel , K. 1983 . Acta Chem. Scand., Ser. A , 37 : 131
  • Almenningen , A. , Haaland , A. and Motzfeldt , T. 1967 . J. Organomet. Chem. , 7 : 97
  • Alkaline-earth compounds are found to have comparably wide errors; e.g., 148(6)° in Cp2∗Ba and 154(3)° in Cp2∗Ca.13
  • Jutzi , P. , Holtmann , U. , Kanne , D. , Krueger , C. , Blom , R. , Gleiter , R. and Hyla , K. I. 1989 . Chem. Ber. , 122 : 1629
  • Glidewell , C. 1985 . J. Organomet. Chem. , 286 : 289
  • Lee , T. J. and Rice , J. E. 1989 . J. Am. Chem. Soc. , 111 : 2011
  • It is ironic that d orbital participation is thought to favor linear structures in the Group 14 metallocenes, whereas it has been used to rationalize bent Group 2 structures. A recent reexamination of the question of d-orbital participation in hypervalent Group 15, 16, and 18 halides has emphasized that the improvement in the energies produced by the inclusion of d-orbital functions in molecular orbital calculations of these compounds is not proof that d-orbitals are directly involved in the bonding. Rather, they can serve as general polarization functions.37 A similar caveat may apply to calculations on main-group metallocenes
  • Cooper , D. L. , Cunningham , T. P. , Gerratt , J. , Karadakov , P. B. and Raimondi , M. 1994 . J. Am. Chem. Soc. , 116 : 4414
  • Dewar , M. J. S. , Grady , G. L. , Kuhn , D. R. and Merz , K. M. Jr. 1984 . J. Am. Chem. Soc. , 106 : 6773
  • Dewar , M. J. S. , Healy , E. F. , Kuhn , D. R. and Holder , A. J. 1991 . Organometallics , 10 : 431
  • Dewar , M. J. S. , Holloway , M. K. , Grady , G. L. and Stewart , J. J. P. 1985 . Organometallics , 4 : 1973
  • Armstrong , D. R. , Herbst-Irmer , R. , Kuhn , A. , Moncrieff , D. , Paver , M. A. , Russell , C. A. , Stalke , D. , Steiner , A. and Wright , D. S. 1993 . Angew. Chem. Int. Ed. Engl. , 32 : 1774
  • The rings in the [Cp2∗As]+ cation, for example, are sufficiently slipped that it is no longer realistic to consider them as pentahapto bonded (a description has been given in terms of a (λ3-Cp∗)As(λ2-Cp∗) structure).44 Although halfsandwich [Cp'PX]+ complexes have been prepared, no isolated examples of the [Cp'2Pj]+ cation are known, and calculations have differed widely on the energetics of the possible conformations.29,34,44 Ab initio calculations favor a non-symmetrical (λ2-Cp)P(λ1-Cp) form as the energy minimum.44
  • Jutzi , P. , Wipperman , T. , Krüger , C. and Kraus , H.-J. 1983 . Angew. Chem. Int. Ed. Engl. , 22 : 250
  • Lee , T. J. , Schaefer , H. F. and Magnusson , E. A. 1985 . J. Am. Chem. Soc. , 107 : 7239
  • Cotton , F. A. and Wilkinson , G. 1988 . Advanced Inorganic Chemistry , New York : Wiley .
  • Williamson , R. L. and Hall , M. B. 1986 . Organometallics , 5 : 2142
  • Bruno , G. , Ciliberto , E. , Fragala , I. L. and Jutzi , P. 1985 . J. Organomet. Chem. , 289 : 263
  • Cradock , S. and Duncan , W. 1978 . J. Chem. Soc. Faraday Trans 11 , 74 : 194
  • Tanner , P. S. and Hanusa , T. P. 1994 . Polyhedron , 13 : 2417
  • Gardiner , M. G. , Hanson , G. R. , Junk , P. C. , Raston , C. L. , Skelton , B. W. and White , A. H. 1992 . J. Chem. Soc. Chem. Commun. , : 1154
  • Harrison , P. G. and Zuckerman , J. J. 1969 . J. Am. Chem. Soc. , 91 : 6885
  • Bos , K. D. , Bulten , E. J. and Noltes , J. G. 1975 . J. Organomet. Chem. , 99 : 397
  • Jutzi , P. , Bunte , E. A. , Holtmann , U. , Neumann , B. and Stammler , H. G. 1993 . J. Organomet. Chem. , 446 : 139
  • Schumann , H. , Janiak , C. and Zuckerman , J. J. 1988 . Chem. Ber. , 121 : 207
  • Harrison , P. G. and Zuckerman , J. J. 1970 . J. Am. Chem. Soc. , 92 : 2577
  • Dory , T. S. , Zuckerman , J. J. and Barnes , C. L. 1985 . J. Organomet. Chem. , 281 : C1
  • Hani , R. and Geanangel , R. A. 1985 . J. Organomet. Chem. , 293 : 197
  • Jutzi , P. and Kohl , F. X. 1981 . Chem. Ber. , 114 : 488
  • Wade , K. 1976 . “Structural and Bonding Patterns in Cluster Chemistry” . In Adv. Inorg. Chem. Radinchem , Vol. 18 , 1 New York : Academic .
  • Mingos , D. M. P. 1972 . Nature (London), Phys. Sci. , 236 : 99
  • Cowley , A. H. , Kemp , R. A. and Stewart , C. A. 1982 . J. Am. Chem. Soc. , 104 : 3239
  • Burns , C. J. and Andersen , R. A. 1987 . J. Organomet. Chem. , 325 : 31
  • Williams , R. A. , Hanusa , T. P. and Huffman , J. C. 1990 . J. Am. Chem. Soc. , 112 : 2454
  • Sockwell , S. C. , Tanner , P. S. and Hanusa , T. P. 1992 . Organometallics , 11 : 2634
  • Tanner , P. S. , Williams , R. A. and Hanusa , T. P. 1993 . Inorg. Chem. , 32 : 2234
  • Adducts of Cp2∗Si with CO and N2 have been identified in liquid xenon (1.5 bar CO, 20 bar N2 respectively).67 They form to an extent of <1% and the adducts readily dissociate when the pressure is released. Their formation does not contradict the general statement that Group 14 metallocenes do not form stable adducts with weak Lewis bases
  • Tacke , M. , Klein , C. , Stufkens , D. J. , Oskam , A. , Jutzi , P. and Bunte , E. A. 1993 . Z. Anorg. Allg. Chem. , 619 : 865
  • Jutzi , P. and Hielscher , B. 1986 . Organometallics , 5 : 1201
  • Although not specifically addressed in the literature, there are two possible reaction sequences that could account for the lack of an observable mono(ring) product (Cp∗SnR): (a) one involving disproportionation, i.e.,
  • Davidson , M. G. , Stalke , D. and Wright , D. S. 1992 . Angew. Chem. Int. Ed. Engl. , 31 : 1226
  • Edwards , A. J. , Paver , M. A. , Raithby , P. R. , Russell , C. A. , Stalke , D. , Steiner , A. and Wright , D. S. 1993 . J. Chem. Soc. Dalton Trans. , : 1465
  • Sockwell , S. C. , Hanusa , T. P. and Huffman , J. C. 1992 . J. Am. Chem. Soc. , 114 : 3393
  • With a melting point of 162–164°C [(i-Pr2N)2PC5H4]2Sn is an exception to this generalization; the extreme bulk and asymmetry of the substituent evidently lead to the formation of a stable lattice.74
  • Cowley , A. C. , Lasch , J. G. , Norman , N. C. , Stewart , C. A. and Wright , T. C. 1983 . Organometallics , 2 : 1691
  • Schmitt , G. and Ozman , S. 1976 . Chem.-Ztg. , 100 : 143
  • Burkey , D. J. , Alexander , E. K. and Hanusa , T. P. 1994 . Organometallics , 13 : 2773
  • Stringfellow , G. B. 1989 . Organometallic Vapor Phase Epitaxy: Theory and Practice , San Diego : Academic .
  • Schumann , H. , Janiak , C. , Hahn , E. , Loebel , J. and Zuckerman , J. J. 1985 . Angew. Chem. Int. Ed. Engl. , 24 : 773
  • Atwood , J. L. , Hunter , W. E. , Cowley , A. H. , Jones , R. A. and Stewart , C. A. 1981 . J. Chem. Soc. Chem. Commun. , : 925
  • Heeg , M. J. , Herber , R. H. , Janiak , C. , Zuckerman , J. J. , Schumann , H. and Manders , W. F. 1988 . J. Organomet. Chem. , 346 : 321
  • Jutzi , P. , Kohl , F. , Hofmann , P. , Krueger , C. and Tsay , Y. H. 1980 . Chem. Ber. , 113 : 757
  • Schumann , H. , Janiak , C. , Hahn , E. , Kolax , C. , Loebel , J. , Rausch , M. D. , Zuckerman , J. J. and Heeg , M. J. 1986 . Chem. Ber. , 119 : 2656
  • Cowley , A. H. , Jutzi , P. , Kohl , F. X. , Lasch , J. G. and Schlüter , N. E. N. C. 1984 . Angew Chem. Int. Ed. Engl. , 23 : 616
  • Duff , A. W. , Hitchcock , P. B. , Lappert , M. F. and Taylor , R. G. 1985 . J. Organomet. Chem. , 293 : 271
  • Gardiner , M. G. , Raston , C. L. and Kennard , C. H. L. 1991 . Organometallics , 10 : 3680
  • Robbins , J. L. , Edelstein , N. , Spencer , B. and Smart , J. C. 1982 . J. Am. Chem. Soc. , 104 : 1882
  • Engelhardt , L. M. , Junk , P. C. , Raston , C. L. and White , A. H. 1988 . J. Chem. Soc. Chem. Commun. , : 1500
  • Fischer , E. O. and Stölzle , G. 1961 . Chem. Ber. , 94 : 2187
  • Jutzi , P. , Dickbreder , R. and Nöth , H. 1989 . Chem. Ber. , 122 : 865
  • Fischer , E. O. and Grubert , H. 1956 . Z. Naturforsch. B , 11B : 423
  • Janiak , C. , Schumann , H. , Stader , C. , Wrackmeyer , B. and Zuckerman , J. J. 1988 . Chem. Ber. , 121 : 1745
  • Fischer , E. O. and Grubert , H. 1956 . Z. Anorg. Allg. Chem. , 286 : 237
  • Jutzi , P. and Dickbreder , R. 1989 . J. Organomet. Chem. , 373 : 301

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