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Microwave Spectrum, Structure, and Dipole Moment of Difluorophosphine Borane
dc.contributor.authorPasinski, John P.en_US
dc.contributor.authorKuczkowski, Robert L.en_US
dc.date.accessioned2010-05-06T23:36:35Z
dc.date.available2010-05-06T23:36:35Z
dc.date.issued1971-03-01en_US
dc.identifier.citationPasinski, John P.; Kuczkowski, Robert L. (1971). "Microwave Spectrum, Structure, and Dipole Moment of Difluorophosphine Borane." The Journal of Chemical Physics 54(5): 1903-1908. <http://hdl.handle.net/2027.42/71354>en_US
dc.identifier.urihttps://hdl.handle.net/2027.42/71354
dc.description.abstractThe structure of difluorophosphine borane (HF2P☒BH3) has been determined from the microwave spectra of six isotopic species. The expected staggered conformation and CsCs symmetry have been confirmed. The structural parameters are: d(PH)  =  1.409 ± 0.004Å;d(PF)  =  1.552 ± 0.006Å;d(PB)  =  1.832 ± 0.009Å;d(BHa)  =  1.226 ± 0.005Å;d(BHs)  =  1.200 ± 0.007Å;∠HaBHa  =  112.7 ± 0.5°;∠HaBHs  =  115.9 ± 0.4°;∠FPF  =  100.0 ± 0.5°;∠FPH  =  98.62 ± 0.25°;∠BPF  =  117.7 ± 0.3°d(PH)=1.409±0.004Å;d(PF)=1.552±0.006Å;d(PB)=1.832±0.009Å;d(BHa)=1.226±0.005Å;d(BHs)=1.200±0.007Å;∠HaBHa=112.7±0.5°;∠HaBHs=115.9±0.4°;∠FPF=100.0±0.5°;∠FPH=98.62±0.25°;∠BPF=117.7±0.3°. Two angles (PBHs  =  109.9 ± 0.3°;PBHa  =  99.89 ± 0.26°)(PBHs=109.9±0.3°;PBHa=99.89±0.26°) indicate a tilt of the borane group away from the fluorine atoms. The value of the dipole moment obtained from Stark splittings is 2.504 ± 0.030 D. A range for the barrier to internal rotation is estimated as 3600–4500 cal/mole. The change in structural parameters of HF2PBH3 compared to similar compounds, the stability of HF2PBH3 towards dissociation, and the tilted borane group are discussed.en_US
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dc.publisherThe American Institute of Physicsen_US
dc.rights© The American Institute of Physicsen_US
dc.titleMicrowave Spectrum, Structure, and Dipole Moment of Difluorophosphine Boraneen_US
dc.typeArticleen_US
dc.subject.hlbsecondlevelPhysicsen_US
dc.subject.hlbtoplevelScienceen_US
dc.description.peerreviewedPeer Revieweden_US
dc.contributor.affiliationumDepartment of Chemistry, The University of Michigan, Ann Arbor, Michigan 48104en_US
dc.description.bitstreamurlhttp://deepblue.lib.umich.edu/bitstream/2027.42/71354/2/JCPSA6-54-5-1903-1.pdf
dc.identifier.doi10.1063/1.1675116en_US
dc.identifier.sourceThe Journal of Chemical Physicsen_US
dc.identifier.citedreferenceR. W. Rudolph and R. W. Parry, J. Am. Chem. Soc. 89, 1621 (1967).en_US
dc.identifier.citedreferenceR. L. Kuczkowski, J. Am. Chem. Soc. 90, 1705 (1968); R. W. Rudolph and R. W. Parry, Inorg. Chem. 4, 1339 (1965).en_US
dc.identifier.citedreferenceL. F. Centofanti and R. L. Kuczkowski, Inorg. Chem. 7, 2582 (1968); L. F. Centofanti and R. W. Parry, 7, 1005 (1968).en_US
dc.identifier.citedreferenceR. L. Kuczkowski and D. R. Lide, Jr., J. Chem. Phys. 46, 357 (1967); R. W. Parry and T. C. Bissot, J. Am. Chem. Soc. 78, 1524 (1956).en_US
dc.identifier.citedreferenceR. W. Rudolph and H. W. Schiller, J. Am. Chem. Soc. 90, 3581 (1968).en_US
dc.identifier.citedreferenceP. C. Maybury and W. S. Koski, J. Chem. Phys. 21, 742 (1953).en_US
dc.identifier.citedreferenceJ. S. Muenter, J. Chem. Phys. 48, 4544 (1968).en_US
dc.identifier.citedreferenceJ. Kraitchman, Am. J. Phys. 21, 17 (1953).en_US
dc.identifier.citedreferenceV. Dunning (private communication).en_US
dc.identifier.citedreferenceY. Morino, K. Kuchitsu, and T. Moritani, Inorg. Chem. 8, 867 (1969).en_US
dc.identifier.citedreferenceR. J. Gillespie, J. Chem. Educ. 47, 18 (1970).en_US
dc.identifier.citedreferenceH. A. Bent, J. Inorg. Nucl. Chem. 19, 43 (1961).en_US
dc.identifier.citedreferenceD. W. J. Cruickshank, J. Chem. Soc. 1961, 5486.en_US
dc.identifier.citedreferenceW. A. G. Graham and F. G. A. Stone, J. Inorg. Nucl. Chem. 3, 164 (1956).en_US
dc.identifier.citedreference(a) Bartell and Su, employing extended Hückel MO calculations, have also pointed out that HF2PHF2P and F3PF3P behave anomalously.15b They showed that the bonded overlap populations normally increased when more electronegative groups were attached to phosphorous except in the case of the PO overlaps in HF2POHF2PO vs F3PO.F3PO. The EHMO calculations by us on HF2P‐BH3HF2P‐BH3 and F3P‐BH3F3P‐BH3 resulted in a slightly greater P‐B bond overlap population for HF2P‐BH3HF2P‐BH3 vs F3PBH3(<1%).F3PBH3(<1%). In contrast to the mechanism suggested in the text, the σ and π contributions in both molecules were essentially the same. (b) L. S. Bartell, S. L. Su, and H. Yow, Inorg. Chem. 9, 1903 (1970).en_US
dc.identifier.citedreferenceL. Pierce, R. G. Hayes, and J. F. Beecher, J. Chem. Phys. 46, 4352 (1967).en_US
dc.identifier.citedreferenceL. C. Krisher and L. Pierce, J. Chem. Phys. 32, 1619 (1960). These authors assumed that the CH3CH3 group was symmetric in HF2Si‐CH3.HF2Si‐CH3. We found that their data can also accommodate a slight tilt ( ∼ 3°)(∼3°) of the CH3CH3 group away from the fluorines. However, the smallness of the effect and consideration of experimental error and vibrational effects make this interpretation less firm than in HF2P‐BH3.HF2P‐BH3.en_US
dc.identifier.citedreferenceJ. D. Swalen and B. P. Stoicheff, J. Chem. Phys. 28, 671 (1958).en_US
dc.identifier.citedreferenceB. Kirtman, J. Chem. Phys. 37, 2516 (1962).en_US
dc.identifier.citedreferenceJ. P. Lowe and R. G. Parr, J. Chem. Phys. 44, 3001 (1966).en_US
dc.identifier.citedreferenceR. G. Shulman and B. P. Dailey, Phys. Rev. 78, 145 (1950).en_US
dc.identifier.citedreferenceC. A. Burrus, J. Chem. Phys. 28, 427 (1958).en_US
dc.owningcollnamePhysics, Department of


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