Molecular structures of tetrafluorodiphosphine and tetrakis(trifluoromethyl)diphosphine by gas-phase electron diffraction

Hodges, H. L.; Su, Lichao; Bartell, Lawrence S.

doi:10.1021/ic50145a033

Cited by 37 publications

(7 citation statements)

References 5 publications

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“…The typical experimental values, which fall in the range 2.20-2.22 A [12], are similar to the sum of the co valent radii [2.20 Ä], A very short P-P distance of 2.14(1) A was observed in the chelate ring of (CO)4Mo(PMe2 • PMe • PMe • PMe2) [13] and a very long P-P distance of 2.281(6) Ä in P2F4 [14]. The P^P coordinate bond length of 2.234(5) in 2 is very similar to the typical value for the o-bond and significantly shorter than that in P2F4.…”

Section: Discussionsupporting

confidence: 53%

The Crystal Molecular Structure of the Adduct of 2,2,2-Trifluoro-4,4,5,5-tetrakis(trifluoromethyl)-l,3,2A 5 -dioxaphospholane with Trimethylphosphine. A Strong P → P Coordinate Bond

Sheldrick

Gibson

Röschenthaler

1978

Zeitschrift Für Naturforschung B

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Abstract The adduct of 2,2,2-trifluoro-4,4,5,5-tetrakis(trifluoromethyl)-1,3,2 A 5 -dioxaphospholane with trimethylphosphine crystallises in the orthorhombic space group Pbcm, Z = 4, with a - 11.018(2), b - 12.978(4), c= 11.607(2) Å at -120 °C. The perfluoropinacolyl ring system lies in a crystallographic plane of symmetry. This ring conformation and the very long endocyclic C-C bond and average C-CF3 distances of respectively 1.59(1) and 1.59(1) A are presumably a consequence of very short F···F steric contacts. The P→P bond distance of 2.234(5) is very short for a coordinate bond being only 0.01-0.03 A longer than that typically observed for a a-bond. The tr-bond lengths to the hexacoordinate phosphorus are influenced by the nature of the Zrans-bond in the octahedron.

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Section: Discussionsupporting

confidence: 53%

The Crystal Molecular Structure of the Adduct of 2,2,2-Trifluoro-4,4,5,5-tetrakis(trifluoromethyl)-l,3,2A 5 -dioxaphospholane with Trimethylphosphine. A Strong P → P Coordinate Bond

Sheldrick

Gibson

Röschenthaler

1978

Zeitschrift Für Naturforschung B

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“…At the same time, it is known that (CH 3 ) 2 PP(CH 3 ) 2 41,43 and (CF 3 ) 2 PP(CF 3 ) 2 39 in the crystal exist only in the anti-conformation, and this conformer is also dominant in the gas phase, and only the anti-conformation of F 2 PPF 2 was found experimentally. 37,38 These trends are qualitatively reproduced only by B3PW91/augcc-pVTZ computations, which predict the energy of the anticonformer to be lower than the energy of the gauche-form. All other methods we used predict the lower energy for the gaucheconformation.…”

Section: Validation Of the Methodsmentioning

confidence: 99%

Comparative studies of geometric and quasielastic characteristics of PP and SS bonds

Katsyuba

Schmutzler

2008

Dalton Trans.

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It is demonstrated that density functional theory in B3PW91/aug-cc-pVTZ formulation provides a reasonable estimate of the geometrical and vibrational parameters of various PP and SS bonds. Calculated quasielastic characteristics of SS bonds, such as relaxed force constants f(SS), are approximately twice as large as f(PP). This means much higher elasticity of the PP bond, compared to the SS bond. From the dependence of the relaxed force constants on the formal bond order, the various PP bonds studied represent single bonds. By contrast, the more than twice as high rigidity of the SS bonds implies multiple SS bonding. Pronounced shortening of the SS bond on passing from less electronegative to more electonegative substituents at the sulfur atoms can be ascribed to the corresponding increase of the SS pi interactions. Essentially single PP bonds are not affected by electronic effects of this kind, which is the reason for the small variability of PP bond lengths in the gas phase. At the same time, intermolecular forces acting in crystals may strongly influence the length of highly elastic PP bonds.

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“…a Taken from Ref. [5]. b Multi = 1D:CCSD(T)-2D:CCSD-3D:MP2 avtz = aug-cc-pVTZ; acvtz = aug-cc-p[C]VTZ (see text).…”

Section: Fundamental Modesmentioning

confidence: 99%

“…The conformational space of tetrafluorodiphosphine, P 2 F 4 , has been a matter of debate until vibrational spectroscopy in combination with ab initio calculations showed, that the trans conformer is the most stable structure [1][2][3][4][5][6][7][8][9][10][11][12]. Within this context Durig and Shen [8] determined the gauche conformer to be 2.3 kcal/mol higher in energy at the MP2/6-311 + G * level which readily explains the experimental observations.…”

Section: Introductionmentioning

confidence: 99%

A combined variational and perturbational study on the vibrational spectrum of P2F4

Rauhut

Hrenar

2008

Chemical Physics

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Molecular structures of tetrafluorodiphosphine and tetrakis(trifluoromethyl)diphosphine by gas-phase electron diffraction

Cited by 37 publications

References 5 publications

The Crystal Molecular Structure of the Adduct of 2,2,2-Trifluoro-4,4,5,5-tetrakis(trifluoromethyl)-l,3,2A 5 -dioxaphospholane with Trimethylphosphine. A Strong P → P Coordinate Bond

The Crystal Molecular Structure of the Adduct of 2,2,2-Trifluoro-4,4,5,5-tetrakis(trifluoromethyl)-l,3,2A 5 -dioxaphospholane with Trimethylphosphine. A Strong P → P Coordinate Bond

Comparative studies of geometric and quasielastic characteristics of PP and SS bonds

A combined variational and perturbational study on the vibrational spectrum of P2F4

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