메뉴 건너뛰기




Volumn 23, Issue 17 SPEC.ISS., 2004, Pages 2879-2900

Theoretical investigation of the metal-metal interaction in dimolybdenum complexes with bridging hydride and methyl ligands

Author keywords

[No Author keywords available]

Indexed keywords

ATOMS; BINARY ALLOYS; DENSITY FUNCTIONAL THEORY; HYDRIDES; LIGANDS; MOLYBDENUM COMPOUNDS;

EID: 8644235707     PISSN: 02775387     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.poly.2004.08.004     Document Type: Conference Paper
Times cited : (47)

References (151)
  • 1
    • 0042094289 scopus 로고
    • The "18-electron rule" is variously referred to as "effective atomic number rule", "inert gas rule" and "rare gas rule" in the literature. For reviews of the 18-electron rule, see: P.R. Mitchell, and R.V. Parish J. Chem. Educ. 46 1969 811
    • (1969) J. Chem. Educ. , vol.46 , pp. 811
    • Mitchell, P.R.1    Parish, R.V.2
  • 5
    • 85168785380 scopus 로고    scopus 로고
    • in press
    • For a discussion of the 18-electron rule in terms of the Complementary Spherical Electron Density Model, see: (a) D.M.P. Mingos, J. Organomet. Chem. (2004), in press
    • (2004) J. Organomet. Chem.
    • Mingos, D.M.P.1
  • 12
    • 0039860367 scopus 로고
    • For a brief overview of 3-center-2-electron interactions, see: R.L. DeKock, and W.B. Bosma J. Chem. Ed. 65 1988 194
    • (1988) J. Chem. Ed. , vol.65 , pp. 194
    • Dekock, R.L.1    Bosma, W.B.2
  • 18
    • 85168790374 scopus 로고    scopus 로고
    • note
    • - ligands equally to each metal, i.e. the anion contributes 1 electron to the electron count of each metal center, both of which bear a +0.5 charge
  • 21
    • 85168792999 scopus 로고    scopus 로고
    • note
    • 3 fragments. Specifically, the "open" B-B-B interaction employs a p-orbital on the central boron, such that the outer boron atoms are required by symmetry arguments to exhibit an out-of-phase antibonding interaction. For situations with a bridging hydrogen atom, the two outer atoms will always exhibit a bonding interaction, and the classification of "open" and "closed" relates to the magnitude of the interaction. See [12,13]
  • 27
    • 0001628896 scopus 로고
    • This notation was first introduced to describe B-H-B interactions. See: R.W. Parry, and G. Kodama Coord. Chem. Rev. 128 1993 245
    • (1993) Coord. Chem. Rev. , vol.128 , pp. 245
    • Parry, R.W.1    Kodama, G.2
  • 33
    • 85168785007 scopus 로고    scopus 로고
    • note
    • - fragment
  • 53
    • 0000275676 scopus 로고
    • + adopting a monohapto agostic interaction, see: B.E. Bursten, and R.H. Cayton Organometallics 5 1986 1051 and references therein
    • (1986) Organometallics , vol.5 , pp. 1051
    • Bursten, B.E.1    Cayton, R.H.2
  • 62
    • 0141479168 scopus 로고
    • Indeed, the metal-metal separation in dinuclear complexes with bridging ligands and no metal-metal bond may be shorter than unbridged complexes with a metal-metal bond. See, for example: H. Vahrenkamp Angew. Chem., Int. Ed. Engl. 17 1978 379
    • (1978) Angew. Chem., Int. Ed. Engl. , vol.17 , pp. 379
    • Vahrenkamp, H.1
  • 67
    • 85168784908 scopus 로고    scopus 로고
    • note
    • Note that these specific compounds have been selected because the bond order assignment is independent of electron count method used because none of the bridges are involved in 3-center-2-electron interactions
  • 68
    • 85168788613 scopus 로고    scopus 로고
    • note
    • 2 configuration results such that the Mo-Mo bond order is zero. See [45]
  • 78
    • 85168791908 scopus 로고    scopus 로고
    • note
    • Wiberg's bond index is often denoted as P. We use W to avoid confusion with the density matrix, which is widely abbreviated as P, as we do here
  • 84
    • 85168786065 scopus 로고    scopus 로고
    • note
    • There are five more unoccupied metal-dominated MOs to complete the set of 10 MOs relevant for the dimetallic complex, all of which are indicated in Fig. 11. However, because they are not of much significance for the goal of this investigation, they are not further discussed
  • 85
    • 8644235229 scopus 로고
    • Specifically, the ionization bands assigned to the M(μ-H)M interactions showed a marked variation in intensity in the HeI and HeII spectra, indicating a significant contribution from the hydrogen 1s orbital which is known to be sensitive to such changes: J.C. Green, D.M. Mingos, and E.A. Seddon Inorg. Chem. 20 1981 2595
    • (1981) Inorg. Chem. , vol.20 , pp. 2595
    • Green, J.C.1    Mingos, D.M.2    Seddon, E.A.3
  • 89
    • 0004233970 scopus 로고
    • 2nd ed. VCH New York
    • 2M] bond and one 2-centered M-M bond. However, a double 2-centered-2-electron MM interaction is not a viable alternative since there would be no orbitals available on M for interaction with the hydrogen atoms. See, for example: C. Elschenbroich, and A. Salzer Organometallics 2nd ed. 1992 VCH New York p. 79
    • (1992) Organometallics
    • Elschenbroich, C.1    Salzer, A.2
  • 107
    • 0001047625 scopus 로고    scopus 로고
    • 3CO where the apparently >18electron count is deceiving because one of the ligand orbital combinations remains nonbonding as a result of there being no metal based orbital of appropriate symmetry with which to interact; the electron count at the metal in such complexes is thus reduced from 20 to 18. See, for example: H. Jacobsen, H. Berke, T. Brackemeyer, T. Eisenblätter, G. Erker, R. Fröhlich, O. Meyer, and K. Bergander Helv. Chim. Acta 81 1998 1692
    • (1998) Helv. Chim. Acta , vol.81 , pp. 1692
    • Jacobsen, H.1    Berke, H.2    Brackemeyer, T.3    Eisenblätter, T.4    Erker, G.5    Fröhlich, R.6    Meyer, O.7    Bergander, K.8
  • 121
    • 85168778045 scopus 로고
    • 4 was originally reported in an incorrect space group. See: R.E. Marsh Organometallics 8 1989 1583
    • (1989) Organometallics , vol.8 , pp. 1583
    • Marsh, R.E.1
  • 126
    • 0003438540 scopus 로고
    • 3rd ed. Cornell University Press Ithaca, NY
    • The formal charge (FC) of an atom in a given Lewis structure is the charge it would possess if the electrons in each covalent bond were to be distributed equally between the two bonded atoms such that each partner receives one electron. The notion of formal charge as disussed by Pauling is based on Langmuir's residual charge concept. L. Pauling The Nature of The Chemical Bond 3rd ed. 1960 Cornell University Press Ithaca, NY p. 9
    • (1960) The Nature of the Chemical Bond
    • Pauling, L.1
  • 131
    • 0035569080 scopus 로고    scopus 로고
    • Furthermore, it is well known that the charge on an atom generally bears no relationship to oxidation state. For a brief discussion, including the problem with actually calculating the charge, see: R. Hoffmann Am. Sci. 89 2001 311
    • (2001) Am. Sci. , vol.89 , pp. 311
    • Hoffmann, R.1
  • 132
    • 0000441172 scopus 로고    scopus 로고
    • Bulky substituents on the cyclopentadienyl rings enable the isolation of monomeric zirconocene hydride complexes. See, for example: P.J. Chirik, M.W. Day, and J.E. Bercaw Organometallics 18 1999 1873
    • (1999) Organometallics , vol.18 , pp. 1873
    • Chirik, P.J.1    Day, M.W.2    Bercaw, J.E.3
  • 133
    • 33947435455 scopus 로고
    • 2 that would be predicted using a "half-electron" counting method. The bonding in diborane was initially described as a "protonated double bond". See: K.S. Pitzer J. Am. Chem. Soc. 67 1945 1126
    • (1945) J. Am. Chem. Soc. , vol.67 , pp. 1126
    • Pitzer, K.S.1
  • 134
    • 85168777191 scopus 로고    scopus 로고
    • note
    • s is the number of BHB bridge bonds, t the number of BBB three-center bonds, y number of B-B single bonds, and x is the number of terminal B-H groups
  • 136
    • 0004160492 scopus 로고    scopus 로고
    • Schrödinger, Inc., Portland, OR
    • Jaguar 4.1; Schrödinger, Inc., Portland, OR, 2000
    • (2000) Jaguar 4.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.