The crystal stucture of the nitric acid adducts of triphenylarsine oxide and triphenylphosphine oxide

Batt, Ruth V.; Bullivant, David P.; Elkington, Kathryn E.; Hill, Sally E.; Hilton, Jack; Houghton, Timothy; Hovell, Maurice; Wallwork, S. C.

doi:10.1016/s0277-5387(98)00060-6

Cited by 3 publications

(5 citation statements)

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“…Feature ii points to a differential Δ H ⧧ component to rate differences in the systems [MX‘/O] versus [MX‘/S], which could reflect strengths of M···QAsPh 3 bond-making or As-Q bond-weakening in the transition state. As one measure of basicity, we note that Ph 3 AsO is readily protonated and that As−O bond lengths in various (Ph 3 AsOH) + salts (1.69−1.73 Å) − exceed that in Ph 3 AsO by ca. 0.04−0.08 Å.…”

Section: Resultsmentioning

confidence: 90%

Comparative Kinetics and Mechanism of Oxygen and Sulfur Atom Transfer Reactions Mediated by Bis(dithiolene) Complexes of Molybdenum and Tungsten

et al. 2004

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Although the kinetics and mechanism of metal-mediated oxygen atom (oxo) transfer reactions have been examined in some detail, sulfur atom (sulfido) transfer reactions have not been similarly scrutinized. The reactions [M(IV)(O-p-C(6)H(4)X')(S(2)C(2)Me(2))(2)](1-) + Ph(3)AsQ --> [M(VI)Q(O-p-C(6)H(4)X')(S(2)C(2)Me(2))(2)](1-) + Ph(3)As (M = Mo, W; Q = O, S) with variable substituent X' have been investigated in acetonitrile in order to determine the relative rates of oxo versus sulfido transfer at constant structure (square pyramidal) of the atom acceptor and of atom transfer at constant structure of the atom donor and metal variability of the atom acceptor. All reactions exhibit second-order kinetics and entropies of activation (-25 to -45 eu) consistent with an associative transition state. At parity of atom acceptor, k(2)(S) (0.25-0.75 M(-1)s(-1)) > k(2)(O) (0.023-0.060 M(-1)s(-1)) with M = Mo and k(2)(S) (4.1-66.7 M(-1)s(-1)) > k(2)(O) (1.8-9.8 M(-1)s(-1)) with M = W. At constant atom donor and X', k(2)(W) > k(2)(Mo) with reactivity ratios k(2)(W)/k(2)(Mo) = 78-184 (Q = O) and 16-89 (Q = S). Rate constants refer to 298 K. At constant M and Q, rates increase in the order X' = Me less, similar OMe < H < Br < COMe < CN; increasing electron-withdrawing propensity accelerates reaction rates. The probable transition state involves significant Ph(3)AsQ...M bond-making (X' rate trend) and concomitant As-Q bond weakening (bond energy order As-O > As-S). Orders of oxo and sulfido donor ability of substrates and complexes are deduced on the basis of qualitative reactivity properties determined here and elsewhere. This work complements previous studies of the reaction systems [M(IV)(O-p-C(6)H(4)X')(S(2)C(2)Me(2))(2)](1-)/XO where the substrates are N-oxides and S-oxides and k(2)(W) > k(2)(Mo) at constant substrate also applies. The reaction order of substrates is Me(3)NO > (CH(2))(4)SO > Ph(3)AsS > Ph(3)AsO. This research provides the first quantitative information of metal-mediated sulfido transfer.

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Section: Resultsmentioning

confidence: 90%

Comparative Kinetics and Mechanism of Oxygen and Sulfur Atom Transfer Reactions Mediated by Bis(dithiolene) Complexes of Molybdenum and Tungsten

et al. 2004

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“…In the issue of covalency, a very high | V ( r )|/ G ( r ) value exceeding 2.0 as well as a negative ∇ 2 ρ( r ) value for the O–H···O interaction in TPPO.nitric acid cocrystal (QTAIM analysis, vide Table ) corroborate the NBO results. From X-ray diffraction study, it has been authenticated that the O (TPPO) ···H + and O (nitrate) ···H + distances, 1.352 and 1.303 Å respectively, do not largely differ and the O (TPPO) ···H + ···O (nitrate) contact is bent (143°). As suggested by the Mayer bond orders: 0.29 for O (TPPO) ···H + and 0.50 for O (nitrate) ···H + interactions, a moderately strong 3c–4e bonding can be invoked to model the electron delocalization occurring in the bent O (TPPO) ···H + ···O (nitrate) motif.…”

Section: Resultsmentioning

confidence: 99%

“…In the issue of covalency, a very high |V(r)|/ G(r) value exceeding 2.0 as well as a negative ∇ 2 ρ(r) value for the O−H•••O interaction in TPPO.nitric acid cocrystal (QTAIM analysis, vide Table 1) corroborate the NBO results. From X-ray diffraction study, 19…”

Section: Nbo Analysismentioning

confidence: 99%

“…By subsequently including apposite TPPO cocrystals of increasingly acidic H-bond donors, we can create a diverse set of donor–acceptor compounds to pursue a coherent analysis of the O–H···O interactions. In order to accomplish the objective, we have selected 11 TPPO cocrystals − along with the TPPO.hemihydrate polymorphs to render the sample size and quality statistically acceptable (17 O–H···O interactions, Table ) on the basis of the following factors: (i) varying geometrical attributes of the H-bonds (Table ), (ii) different acidic H-bond donors, and (iii) inclusion of the covalent O–H···O interaction.…”

Section: Introductionmentioning

confidence: 99%

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Noncovalent and Covalent O–H···O Interactions in PPh₃O Cocrystals: A Correlation Study Involving QTAIM, SAPT, NBO, and IBSI Methods

Sen,

Sinha,

Banerjee

et al. 2024

ACS Omega

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PPh3O.hemihydrate polymorphs and 11 assorted PPh3O cocrystals collectively constitute a reliable stock to pursue a systematic analysis aiming to investigate the impacts of some vital issues on the TPPO.H-bond donor aggregates. The issues highlighted herein are (i) effect of varying acidity of H-bond donors on the degeneracy of lone pairs of the H-bond acceptor (PPh3O), (ii) effectiveness of the |V(r)|/G(r) and H(r)/ρ(r) parameters as a covalency metric, (iii) 3c–4e bonding in the covalent PPh3O.nitric acid cocrystal, (iv) salient features of H-bond interaction energy and an interplay of its components, (v) an intrinsic bond strength scale for the PPh3O cocrystals, and (vi) reliable empirical relations between several bond descriptors for a quick estimation of interaction energy. To be specific about point (vi), we have propounded two promising avenues for a fast semiquantitative calculation of interaction energy from an endearing nonenergetic parameter, viz., bond length: dO–H···O → ρBCP (MAPE = 2.36%) → E SAPT0 (MAPE = 9.26%), and dO–H···O → IBSI (MAPE = 1.87%) → E SAPT0 (MAPE = 9.66%). All the aforesaid issues have been explored in detail through the QTAIM, NBO, and IBSI analyses (M06-2X-D3/def2-TZVP level), as well as by the SAPT study at the SAPT0/aug-cc-pVDZ platform. The statistically valid correlation studies can be particularly conducive for practical purposes as a transformative extension of the established facts into postulates for the unknown cocrystals.

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“…When this reaction is repeated with N 2 O 3 in excess, and in rigorously dry conditions, the result is precipitate of a triphenylphosphine adduct. However, the presence of small amounts of moisture will cause the formation of a second product as a waxy yellow, slowly crystallizing solid, an adduct of nitric acid and triphenylphosphine oxide, Tranter's salt,, , [Ph 3 P=O][HONO 2 ]. IR: ν̃ = 3084, 3060, 1635 (br), 1438, 1422, 1285, 1249, 1120 (s), 1051, 947, 725, 693, 536 cm –1 .…”

Section: Methodsmentioning

confidence: 99%

Isolable Adducts of Tertiary Amines and Dinitrogen Trioxide

Rosadiuk

Bohle

2018

Eur J Inorg Chem

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Anhydrous dinitrogen trioxide, N 2 O 3 , dissolved in toluene or dichloromethane rapidly forms stable adducts with tertiary amines such triethyl-, tribenzyl-, or trihexyl-amine. With DABCO, 1,4-diazabicyclo[2.2.2]octane it forms a free flowing orange solid. The analytical and spectroscopic data for the DABCO adduct indicate a formula of DABCO(N 2 O 3 ) 2 which has been characterized by IR, Raman, and UV/Vis spectroscopy. The R 3 N-N 2 O 3 adducts are hydrolytically sensitive oils or solids which rapidly react quantitatively with thiols to give RSNO. The reac- [a]

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The crystal stucture of the nitric acid adducts of triphenylarsine oxide and triphenylphosphine oxide

Cited by 3 publications

References 4 publications

Comparative Kinetics and Mechanism of Oxygen and Sulfur Atom Transfer Reactions Mediated by Bis(dithiolene) Complexes of Molybdenum and Tungsten

Comparative Kinetics and Mechanism of Oxygen and Sulfur Atom Transfer Reactions Mediated by Bis(dithiolene) Complexes of Molybdenum and Tungsten

Noncovalent and Covalent O–H···O Interactions in PPh₃O Cocrystals: A Correlation Study Involving QTAIM, SAPT, NBO, and IBSI Methods

Isolable Adducts of Tertiary Amines and Dinitrogen Trioxide

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The crystal stucture of the nitric acid adducts of triphenylarsine oxide and triphenylphosphine oxide

Cited by 3 publications

References 4 publications

Comparative Kinetics and Mechanism of Oxygen and Sulfur Atom Transfer Reactions Mediated by Bis(dithiolene) Complexes of Molybdenum and Tungsten

Comparative Kinetics and Mechanism of Oxygen and Sulfur Atom Transfer Reactions Mediated by Bis(dithiolene) Complexes of Molybdenum and Tungsten

Noncovalent and Covalent O–H···O Interactions in PPh3O Cocrystals: A Correlation Study Involving QTAIM, SAPT, NBO, and IBSI Methods

Isolable Adducts of Tertiary Amines and Dinitrogen Trioxide

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Noncovalent and Covalent O–H···O Interactions in PPh₃O Cocrystals: A Correlation Study Involving QTAIM, SAPT, NBO, and IBSI Methods