Theoretical studies of diphosphene and diphosphinylidene in their closed-shell states, low-lying open-shell singlet and triplet states, and transition states.  Search for a stable bridged structure

Allen, Thomas L.; Scheiner, Andrew C.; Yamaguchi, Yukio; Schaefer, Henry F.

doi:10.1021/ja00284a023

Cited by 45 publications

(31 citation statements)

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“…The HOMO and HOMO-1 are separated by 0.56 eV in the planar molecule, in good agreement with Allen et al 58, and are stabilized roughly in parallel across the range of τ 1 = τ 2 angles. The stabilization fits a cos 2 τ (τ = τ 1 = τ 2 ) dependence (r 2 > 0.99), indicating that π-π overlap between the ring and central -P=P- is the prevailing influencing factor.…”

Section: Resultssupporting

confidence: 88%

Twisting the Phenyls in Aryl Diphosphenes (Ar−P═P−Ar). Significant Impact upon Lowest Energy Excited States

et al. 2009

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Aryl diphosphenes (Ar-P=P-Ar) possess features that may make them useful in photonic devices, including the possibility for photochemical E-Z isomerization. Development of good models guided by computations is hampered by poor correspondence between predicted and experimental UV/vis absorption spectra. An hypothesis that the phenyl twist angle (i.e. PPCC torsion) accounts for this discrepancy is explored, with positive findings. DFT and TDDFT (B3LYP) were applied to the phenyl-P=P-phenyl (Ph-P=P-Ph) model compound over a range of phenyl twist angles, and to the Ph-P=P-Ph cores of two crystallographically characterized diphosphenes: bis-(2,4,6-tBu 3 C 6 H 2 )-diphosphene (Mes*-P=P-Mes*) and bis-(2,6-Mes 2 C 6 H 3 )-diphosphene (Dmp-P=P-Dmp). A shallow PES is observed: the full range of phenyl twist angles is accessible for under 5 kcal/mol. The KohnSham orbitals (KS-MOs) exhibit stabilization and mixing of the two highest energy frontier orbitals -the n + and π localized primarily on the -P=P-unit. A simple, single-configuration model based upon this symmetry-breaking is shown to be consistent with the major features of the measured UV/ vis spectra of several diphosphenes. Detailed evaluation of singlet excitations, transition energies and oscillator strengths with TDDFT showed that the lowest energy transition (S 1 ← S 0 ) does not always correspond to the LUMO ← HOMO configuration. Coupling between the phenyl rings and central -P=P-destabilizes the π-π* dominated state. Hence, the S 1 is always n + -π* in nature, even with a π-type HOMO. This coupling of the ring and -P=P-π systems engenders complexity in the UV/vis absorption region, and may be the origin of the variety of photobehaviours observed in diphosphenes.

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Section: Resultssupporting

confidence: 88%

Twisting the Phenyls in Aryl Diphosphenes (Ar−P═P−Ar). Significant Impact upon Lowest Energy Excited States

et al. 2009

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“…The parent system PPH 2 along with isomer HP = PH has been the focus of several theoretical studies. [74][75][76][77] The tertbutyl substituted variant, tBu 2 PP, is known in complexes to electronically mimic olefins and in trapping experiments to have singlet phosphinidene character. [78] Singlet phosphinidenes are being sought, and the phosphino substituent has been proposed as one of the most viable for their stabilization.…”

Section: Diorganophosphanylphosphinidenes: Phosphinidenes With a Pr 2mentioning

confidence: 99%

Terminal, Anionic Carbide, Nitride, and Phosphide Transition‐Metal Complexes as Synthetic Entries to Low‐Coordinate Phosphorus Derivatives

Cummins

2006

Angew Chem Int Ed

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Anionic terminal one‐atom nitride, phosphide, and carbide complexes are excellent starting materials for the synthesis of ligands containing low‐coordinate phosphorus centers in the protecting coordination sphere of the metal complex. Salt‐elimination reactions with chlorophosphanes lead to phosphaisocyanide, iminophosphinimide, and diorganophosphanylphosphinidene complexes in which the unusual phosphorus ligands are stabilized by coordination. X‐ray structure analyses and density‐functional calculations illuminate the bonding in these compounds.

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“…Since the first report of diphosphene of which the PdP double bond is kinetically protected by a bulky substituent in 1981, 1 the synthesis, the structures and the reactivity of various double bond compounds of heavier group 15 elements have been examined [2][3][4][5][6] and reviewed as well. [7][8][9] In accordance with realization of this class of compounds, theoretical investigations of the bonding nature and the reactivity of heavier group 15 element compounds have been done, although the oversimplified molecules without substituents were adopted as model compounds in most of calculations 6,[10][11][12][13][14] In the past several years, a new direction, where PdP double bond compounds are intended to be utilized as photofunctional materials of electronic, optical, and magnetic devices, has begun to grow. Yoshifuji and co-workers systematically examined the electronic effects of the substituents on diphosphenes.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Study on the Phenyl Torsional Potentials of trans-Diphenyldiphosphene

Amatatsu

2008

J. Phys. Chem. A

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The phenyl torsional potentials of trans-diphenyldiphosphene ( trans-phosphobenzene; t-DPP), which is an analogue of trans-azobenzene ( t-AZB), have been examined by means of ab initio complete active space self-consistent field (CASSCF) calculations. Though the electronic structures of t-DPP are similar to those of t-AZB, the phenyl torsional potentials are different from each other. In S 0, the potential energy curve of t-DPP has double minima at nonplanar conformations with C 2 and C i symmetries, while that of t-AZB has only minimum at a planar conformation with C 2 h . In S 1, the phenyl torsion of t-AZB is impeded from a planar geometry more than that in S 0. On the other hand, the phenyl torsion of t-DPP is promoted so that the phenyl groups are perpendicularly twisted against the PP double bond around the Franck-Condon region. Comments on the experimental findings of realistic diphosphenes protected by bulky substituents are also made.

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Theoretical studies of diphosphene and diphosphinylidene in their closed-shell states, low-lying open-shell singlet and triplet states, and transition states. Search for a stable bridged structure

Cited by 45 publications

References 0 publications

Twisting the Phenyls in Aryl Diphosphenes (Ar−P═P−Ar). Significant Impact upon Lowest Energy Excited States

Twisting the Phenyls in Aryl Diphosphenes (Ar−P═P−Ar). Significant Impact upon Lowest Energy Excited States

Terminal, Anionic Carbide, Nitride, and Phosphide Transition‐Metal Complexes as Synthetic Entries to Low‐Coordinate Phosphorus Derivatives

Theoretical Study on the Phenyl Torsional Potentials of trans-Diphenyldiphosphene

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