Analysis of the Relative Stabilities of Ortho, Meta, and Para MClY(XC₄H₄)(PH₃)₂Heterometallabenzenes (M = Rh, Ir; X = N, P; Y = Cl and M = Ru, Os; X = N, P; Y = CO)

Abstract

Density functional theory calculations of the relative stabilities of the ortho, meta, and para MClY(XC 4 H 4 )-(PH 3 ) 2 heterometallabenzenes (M = Rh, Ir; X = N, P; Y = Cl and M = Ru, Os; X = N, P; Y = CO) have been carried out. The ortho isomer is the most stable for X = P, irrespective of the metal M. For X = N and M = Ir, Rh the meta is the lowestlying isomer, whereas for M = Ru, Os the ortho and meta isomers are almost degenerate. The electronic structure and chemical bonding have been investigated with energy decomposition analyses of the interaction energy between various fragments, to discuss the origin of the differences observed. The values of the multicenter index of aromaticity and nucleus-independent chemical shifts indicate that the heterometallabenzenes studied should be classified as aromatic or slightly aromatic.

Probing the Origin of Challenge of Realizing Metallaphosphabenzenes: Unfavorable 1,2-Migration in Metallapyridines Becomes Feasible in Metallaphosphabenzenes

“…This could be one of the reasons why some metallapyridines have been isolated whereas metallaphosphabenzenes have never been synthesized. Apparently, the stability of iridaphosphabenzenes and iridapyridines relative to their nonaromatic analogues increases dramatically in comparison with rhodaphosphabenzenes and rhodapyridines due to more diffuse d orbitals, in line with previous results that 5 d metallacycles are more stable than their 4 d analogues12319. These results are also applicable to ruthenaphosphabenzenes and osmaphosphabenzenes (Fig.…”

“…In contrast, the heteroatom-containing metallabenzenes such as metallapyrylium910, metallathiabenzene1112, metallapyridine1314, metallapyrrole1516, and metallathiophene1718 are relatively less developed. To the best of our knowledge, metallaphosphabenzene has not been synthesized so far, although its structure and property were investigated theoretically1920. The difficulties in the synthesis and isolation of metallaphosphabenzene could be due to the reluctance of phosphorus to participate in multiple bonds21, similar to our previous finding22 that 1,2-migration in metallasilabenzenes becomes favorable due to the reluctance of silicon to participate in π bonding.…”

“…2, 1a – h ) as a phosphorus atom at the ortho position on metallaphosphabenzene, which was reported to be more stable than those at the meta and para positions by Solà and co-workers19. As shown in Fig.…”

Nine questions on energy decomposition analysis

“…Finally, the analysis of isomerization energies can be performed using different fragments. In many cases, one can use the same fragments to build the two isomers just placing them with different orientation (we called this procedure the turn‐upside‐down approach) . With this procedure, one usually gets a deep understanding of the physical origin of the isomerization energy.…”

Solubility prediction of bio-oil derived chemicals in aqueous media by Localized Molecular Orbital-Energy Decomposition Analysis (LMO-EDA) and COSMO-RS predictions

“…Some of the widely used schemes based on the variational approach include the Kitaura-Morokuma (KM) scheme [4,5] which forms the basis for many of the [16] is an extension and modification of the KM scheme. The advantage of this method over KM scheme is that high-level quantum chemistry methods such as MP2, CCSD Due to its simplicity and robustness, the LMO-EDA scheme has been widely used for various weak and strong interactions [25][26][27][28][29][30][31]. Feng Yu [25] has studied the intermolecular interactions between HCOOH and C 6 H 6 with the LMO-EDA method and found that the dispersion energies are as important as the electrostatic energies for the total interaction energies of the five HCOOH…C 6 H 6 complexes.…”