Electronic structure of [M(η-P3C2But2)(CO)3] (M = Mn or Re): a study by photoelectron spectroscopy and density functional calculations

Aromatic λ3 heterocycles XIV. Fosfinine-ether macrocyclesheterocycles XIV. Fosfinine-ether macrocycles

“…The energy of molecular orbitals in phosphinine-ether macrocycles are raised with respect to phosphinine, that is in agreement with previous calculations and photoelectron spectra of substituted phosphabenzene and triphosphabenzene [15,17,18,35]. Table 7 HOMO and LUMO energies and HOMO-LUMO gaps calculated with PM3 and MNDO/d methods in comparison with 2,6-bistrimethylsilil phosphinine (eV) [40,41].…”

“…Molecular orbitals with the same character became more or less stable. Thus, the introduction of tertbutyl group in phosphinine or triphosphinine molecule rise the energies of π and π* levels with the same extent and remote the energies of orbitals [35]. Previous studies showed that electron attracting substituents change the benzophospholide's type of coordination rendering favorable σ coordination [34].…”

“…Previous calculations and photoelectron spectra showed that substitutional pattern influence orbital energies, function of the inductive effect of the substituent [34][35][36]. Molecular orbitals with the same character became more or less stable.…”

The Homoleptic Sandwich Anion [Co(P2C2tBu2)2]−: A Versatile Building Block for Phosphaorganometallic Chemistry

“…Similar cationic ligands have been reported in [CpMoCl(CO){h 3 -P 2 C 2 tBu 2 H(OR)}] (R = H, Me) [16] and [Fe(h 4 -P 3 C 2 tBu 2 nBuMe)(C 5 R 5 )] (R = H, Me), [17] which were prepared by addition of water or methanol to [CpMoCl(CO)(h 4 -P 2 C 2 tBu 2 )] and by lithiation/alkylation of [Fe(h 5 -P 3 C 2 tBu 2 )- (C 5 R 5 )], respectively. [16,18] The distances between the atoms P3, C3, P4, and C4 in 4 (1.776(2)-1.799(2) ) indicate delocalized p-bonding within the P 3 C 2 tBu 2 Ph 2 ligand.…”

Phospha‐Organic Chemistry: Panorama and Perspectives

“…[297] Other recent work includes the synthesis of Ga, In, and Tl derivatives [298,299] and several (h 5 -P 3 C 2 ) metal carbonyl complexes. [300] Several theoretical studies of such complexes are available, [296,299,301,302] one of which explains the diamagnetism of the hexaphosphatitanocene in terms of significant backdonation from the Ti center to the LUMO of the P 3 C 2 ring to form a d bond. [301] 7.…”