TY - JOUR
T1 - Factors affecting metal-metal bonding in the face-shared d3d3 bioctahedral dimer systems, MM′Cl95- (M, M′ = V, Nb, Ta)
AU - Petrie, Simon
AU - Stranger, Robert
PY - 2002/12/2
Y1 - 2002/12/2
N2 - Density functional theory (DFT) calculations have been used to investigate the d3d3 bioctahedral complexes, MM′Cl95-, of the vanadium triad. Broken-symmetry calculations upon these species indicate that the V-containing complexes have optimized metal-metal separations of 3.4-3.5 Å, corresponding to essentially localized magnetic electrons. The metal-metal separations in these weakly coupled dimers are elongated as a consequence of Coulombic repulsion, which profoundly influences (and destabilizes) the gas-phase structures for such dimers; nevertheless, the intermetallic interactions in the V-containing dimers involve significantly greater metal-metal bonding character than in the analogous Cr-containing dimers. These observations all show good agreement with existing experimental (solid state) results for the chloride-bridged, face-shared dimers V2Cl95- and V2Cl3(thf)6+. In contrast to the V-containing dimers, complexes featuring only Nb and Ta have much shorter intermetallic distances (∼2.4 Å) consistent with d-electron delocalization and formal metal-metal triple bond formation; again, good agreement is found with available experimental data. Calculations on the complexes V2(μ-Cl)3(dme)6+, Nb2(μ-dms)3Cl62-, and Ta2(μ-dms)3Cl62-, which are closely related to compounds for which crystallographic structural data exist, have been pursued and provide an insight into the intermetallic interactions in the experimentally characterized complexes. Analysis of the contributions from d-orbital overlap (Eovlp) stabilization, as well as spin polarization (exchange) stabilization of localized d electrons (Espe), has also been attempted for the MM′Cl95- dimers. While Eovlp clearly dominates over Espe as a stabilizing factor in those dimers containing only Nb and Ta metal atoms, detailed assessment of the competition between Eovlp and Espe for V-containing dimers is obstructed by the instability of triply bonded V-containing dimers against Coulombic explosion. On the basis of the periodic trends in Eovlp versus Espe, the V-triad dimers have a greater propensity for metal-metal bonding than do their Cr-triad or Mn-triad counterparts.
AB - Density functional theory (DFT) calculations have been used to investigate the d3d3 bioctahedral complexes, MM′Cl95-, of the vanadium triad. Broken-symmetry calculations upon these species indicate that the V-containing complexes have optimized metal-metal separations of 3.4-3.5 Å, corresponding to essentially localized magnetic electrons. The metal-metal separations in these weakly coupled dimers are elongated as a consequence of Coulombic repulsion, which profoundly influences (and destabilizes) the gas-phase structures for such dimers; nevertheless, the intermetallic interactions in the V-containing dimers involve significantly greater metal-metal bonding character than in the analogous Cr-containing dimers. These observations all show good agreement with existing experimental (solid state) results for the chloride-bridged, face-shared dimers V2Cl95- and V2Cl3(thf)6+. In contrast to the V-containing dimers, complexes featuring only Nb and Ta have much shorter intermetallic distances (∼2.4 Å) consistent with d-electron delocalization and formal metal-metal triple bond formation; again, good agreement is found with available experimental data. Calculations on the complexes V2(μ-Cl)3(dme)6+, Nb2(μ-dms)3Cl62-, and Ta2(μ-dms)3Cl62-, which are closely related to compounds for which crystallographic structural data exist, have been pursued and provide an insight into the intermetallic interactions in the experimentally characterized complexes. Analysis of the contributions from d-orbital overlap (Eovlp) stabilization, as well as spin polarization (exchange) stabilization of localized d electrons (Espe), has also been attempted for the MM′Cl95- dimers. While Eovlp clearly dominates over Espe as a stabilizing factor in those dimers containing only Nb and Ta metal atoms, detailed assessment of the competition between Eovlp and Espe for V-containing dimers is obstructed by the instability of triply bonded V-containing dimers against Coulombic explosion. On the basis of the periodic trends in Eovlp versus Espe, the V-triad dimers have a greater propensity for metal-metal bonding than do their Cr-triad or Mn-triad counterparts.
UR - http://www.scopus.com/inward/record.url?scp=0037010988&partnerID=8YFLogxK
U2 - 10.1021/ic011250z
DO - 10.1021/ic011250z
M3 - Article
SN - 0020-1669
VL - 41
SP - 6291
EP - 6297
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 24
ER -