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Inorg. Chem. 1990, 29, 1930-1936 Contribution from the Departments of Chemistry, University of California, Davis, California 95616, and University of California, Berkeley, California 94720, and Center for Computational Quantum Chemistry," School of Chemical Sciences, University of Georgia, Athens, Georgia 30602
Theoretical Studies of Borylphosphine, Its Conjugate Base, and the Lithium Salt of Its Conjugate Base. The Use of Orbital Kinetic Energies To Determine the Origin of the Driving Force for Changes in Molecular Geometry Thomas L. Allen,*,+ Andrew C. Scheiner,t§ and Henry F. Schaefer III1.s Receioed August 17, 1989 We have studied the ground states of BH2PH2,BH2PH-, and BH2PHLi by the methods of ab initio molecular electronic structure theory using a basis set of high quality. While almost nothing is known experimentally about these molecules, they provide useful models for extensive recent experimental work on a series of organic derivatives. For each molecule, we have predicted its molecular geometry, energy, dipole moment, net atomic charges, bond orders, normal vibrational modes, and harmonic vibrational frequencies. The BH2PH2molecule is nonplanar with a 70' out-of-plane angle at phosphorus and an energy 5.9 kcal/mol below the planar form. On going from the planar to the nonplanar form, the B-P bond order of BH2PH2drops from 1.46 to 1 . I 5 (Mayer method) or from 1.64 to 1.35 (Natiello and Medrano method). A study of orbital kinetic energies shows that a shift of one pair of electrons from a weak B-P 7 bond to a much more stable lone pair on phosphorus provides the main driving force for distortion from planarity. The BH2PH- anion is planar with a small BPH angle (100') and a proton affinity of 15.2 eV. Nonplanar BH2PHLi lies in a very shallow potential well, 2.1 kcal/mol below the planar form. It may be described as an approximately planar BH2PHanion with an Li' cation at an out-of-plane angle of 56O. Our results for these molecules are compared with experimental data for their derivatives with alkyl and aryl substituents and for the BH2NH2molecule.
Introduction Inorganic analogues of the ethylene molecule are important in chemistry both for their intrinsic interest and for the insights they provide into t h e nature of t h e double bond. While boranamine (also called aminoborane), BH,NH,, has been extensively studied, except for several theoretical investigations' nothing seems to be known of t h e phosphorus analogue borylphosphine (also called phosphinoborane), BH2PH2. T h e r e have been several studies of its organic derivatives. Evidence for formation of t h e compound Me2BPHzwas obtained by Burg and Wagner., Coates and Livingstone3 have synthesized several compounds with aryl substituents, such as Ph,BPPh,, and characterized them as to dipole moment, B-P stretching frequency, solubility, and degree of association in aromatic solvents. Recently t h e crystal structure of an organic derivative, MeszBPPh2, was determined by Feng, Olmstead, and Power.4 Bartlett, Feng, Dias, and PowerS also determined t h e crystal structures of ion pairs containing t h e Mes,BPR- anion (which may be viewed as a derivative of borylphosphine's conjugate base, BH,PH-) as well a s complexes of this anion a n d related anions with t h e cation Li( EtzO),+. These compounds exhibit several interesting stereochemical features. To understand the chemical bonding and molecular geometries of compounds of these types, we have undertaken a detailed and comprehensive theoretical inquiry into the "parent" molecule with hydrogen atoms in place of t h e organic groups, using a basis set of high quality. In spite of t h e enormous differences in size, we find a remarkably close similarity in many aspects of t h e stereochemistry of BH2PH2and its organic derivatives. Of course, it would be of interest to compare our results with experimental measurements on the hydrogen compounds, but as far a s we can determine, these compounds have yet t o be synthesized.
Method With use of the restricted self-consistent-field (SCF) method, the molecular geometry was optimized by an analytic gradient method6 until the magnitude of each force (Cartesian and internal coordinate) was less than 1 X hartree/bohr. The following basis sets were used: (a) The DZ set is the contracted double-{ Gaussian basis set of Huzinaga, Dunning, and Hay7" with the hydrogen functions scaled by a factor of 1.2. (b) The DZ + P set was formed by adding to the DZ set six d functions ( a = 0.7) for B, six d functions ( a = 0.5) for P, and three p functions ( a = 0.75) for each H, and for Li, the 10s/4s basis set of
'University of California, Davis. University of California, Berkeley. 8 University of Georgia. IIContribution CCQC No. 18. f
0020-1669/90/ 1329-1930$02.50/0
Dunning'O combined with 4p/2p functions consisting of one contracted set of Gaussian functions (exponents 1.488, 0.2667, and 0.07201 with corresponding coefficients of 0.03877,0.236257, and 0.830448) and one set of Gaussians with exponent 0.0237 was used. This basis set is designated B(9~5pld/4s2pld),P(l ls7pld/6s4pld), H(4slp/2slp), Li(IOs4p/4s2p). (c) The DZ + 2P + diff set was formed by adding to the DZ basis set one s function (a = 0.019), one set of p functions (a = 0.019), and two sets of d functions (a = 0.45 and 0.95) for B and one s function (a = 0.035), one set of p functions (a = 0.035), and two sets of d functions (a = 0.25 and 0.75) for P and using the DZ P basis set were used to determine the for H. Analytic second harmonic vibrational frequencies and the corresponding normal modes. In determining configuration interaction (CI) wave functions, we froze the filled inner-shell molecular orbitals. Except for this feature, all singly and doubly excited configurations were included (CISD). The Davidson correctionI4 was used to estimate the effect of unlinked quadruple excitations on the molecular energy. (In the following text all energies are Davidson-corrected energies.) The total number of configurations varied from 3284 for planar BH2PH2with the DZ basis set to 42 531 for nonplanar BH2PH2with the DZ + 2P + diff basis set.
+
The BH,PH, Molecule On optimizing the structure of planar BH2PH2(1) (restricted to C, symmetry), we obtained the bond lengths, bond angles, and other properties shown in Table I. Perhaps the most interesting feature of this structure is its imaginary PH2 wagging frequency, indicating a preference for a nonplanar geometry. (Justification for the double bond in 1 and the lone pair in 2 will be given later.) (a) Gropen, 0. J . Mol. Srrucr. 1977, 36, 1 1 1 . (b) Magnusson, E. Tetrahedron 1985, 41, 5235. (c) Magnusson, E. Aust. J . Chem. 1986, 39,735. (d) Baban, J. A,: Roberts, B. P. J . Chem. Soc.. Perkin Trans. 2 1987, 491. Burg, A. B.; Wagner, R. I. J . Am. Chem. SOC.1953, 75, 3872. Coates. G . E.: Livingstone, J. G. J . Chem. Sac. 1961, 1000. Feng, X.: Olmstead, M. M.; Power, P. P. Inorg. Chem. 1986,25,4615. (a) Bartlett, R. A.; Feng, X.; Power, P. P. J . Am. Chem. Soc. 1986, 108, 6817. (b) Bartlett, R. A.; Dias, H. V. R.; Feng, X.; Power, P. P. J . Am. Chem. SOC.1989, 111, 1306. See also (c) Arif, A. M.; Boggs, .I.E.;
Cowley, A. H.; Lee, J.-G.: Pakulski, M.: Power, J. M. J . Am. Chem. SOC.1986, 108,6083. (d) Couret, C.; Escudie, J.; Garrigues, B.; Lazraq, M.; Satge, J. Can. J . Chem. 1987, 65, 1230. Pulay, P. In Modern Theoretical Chemistry; Schaefer, H. F., 111, Ed.; Plenum Press: New York, 1977; Vol. 4, pp 53-183. Huzinaga, S. J . Chem. Phys. 1965, 42, 1293. Dunning, T. H., Jr. J . Chem. Phys. 1970, 53, 2823. Dunning, T. H., Jr.; Hay, P. J. I n ref 6, Vol. 3, pp 1-27. Dunning, T. H., Jr. J . Chem. Phys. 1971, 55, 716. Saxe, P.; Yamaguchi, Y.; Schaefer, H. F., 111. J . Chem. Phys. 1982, 77, 5641. Osamura, Y.; Yamaguchi, Y.; Saxe, P.; Vincent, M. A,; Gaw, J. F.; Schaefer, H. F., 111. Chem. Phys. 1982, 72, 131. Osamura, Y.; Yamaguchi, Y.; Saxe, P.: Fox, D. J.; Vincent, M. A.; Schaefer, H . F., 111. J . Mol. Strucr. 1983, 103, 183. Davidson, E. R. I n The World of Quantum Chemistry: Daudel, R., Pullman, B., Eds.: Reidel: Dordrecht, 1974: p 17.
0 1990 American Chemical Society
Theoretical Studies of Borylphosphine
H
\,B=P,
H
/
Inorganic Chemistry, Vol. 29, No. 10, 1990 1931
H
/H
,B-P,:
H ‘
H’
1
Table 1. Properties of Nonplanar and Planar BHzPHzE nonplanar, ‘A’ planar, ‘A,
lH H’
2
Relaxation of the symmetry to C, leads to a structure of lower energy, 2, with a highly pyramidal phosphorus atom in opposition to a slightly pyramidal boron atom. Its properties are also listed in Table I. With the DZ + 2P + diff basis set, the out-of-plane angles are 70.0’ at phosphorus and 6.0’ at boron. In spite of the rather striking difference between the two structures, the energy difference is only 5.9 kcal/mol. The orbital occupation of the planar molecule is la122a123a121 b,24a121b125a126a122b223b227a122b12 while that of the nonplanar molecule is 1 af22al23aT2 1a’’24a’25a’26a’27a’22a’’ 23a’’28a’29a’2. The lowest unoccupied molecular orbitals (LUMOs) are 3bl and loa’, respectively. For the planar molecule the HOMO and LUMO are assigned to 7 and A* orbitals, respectively. For the nonplanar molecule they are assigned, respectively, to a lone pair orbital and to an unsymmetrical A* orbital that is mainly localized on boron. The reason why this molecule is nonplanar is discussed in a later section.
The BH2PH- Anion Removal of one of the protons bonded to phosphorus leads to the planar anion 3. Its properties are summarized in Table 11.
3 Compared to planar BH2PH2,the most striking difference is the anion’s strong preference for planarity. Not surprisingly, the anion has a high proton affinity (1 5.2 eV with the DZ + 2P + diff basis set). Addition of diffuse functions to the basis set has relatively little effect on the structural parameters or the vibrational frequencies. The most sensitive property studied here is the dipole moment, decreasing from 0.84 to 0.64 D. The reason why this molecule is planar, in contrast to the nonplanar neutral species, is discussed in a later section. The BH,PHLi Molecule Substitution of one of the phosphorus hydrogens of BH2PH2 by lithium produces the salt BH2PHLi, whose geometry was first optimized by assuming planarity, as in structure 4. With the Li
Li
DZ + P basis set, the Li wag frequency is imaginary (94i cm-I), and thus it was necessary to study the nonplanar structure 5. An energy minimum was found having the lithium ion at an angle of 56.1’ relative to the H I B P plane. The H2 and H3 atoms are slightly depressed and raised, respectively, relative to the HIBP plane (H2down 2.6’, H3up 9.7’), so that the Li+ cation is sharply inclined to an approximately planar BH2PH- anion. This structure lies only 2.1 kcal mol-’ below the planar structure, and thus the P-Li bond is an example of a “polytopic bond”, a structural type first identified by Clementi, Kistenmacher, and Popkie in the LiCN-LiNC system.I5 The properties of the planar and non(15)
Clementi, E.;Kistenmacher, H.;Popkie, H.J . Chem. Phys. 1973, 58, 2460.
r,W) re(BH) rem) W’BH) B,(HBH) UBPH) @,(HPH)
&(out of plane at B)b &(out of plane at P)b energy, SCF‘ energy, CISD‘ energy, Davidson cof dipole moment vibrational freq, u, asym BH str sym BH str asym PH str sym PH str sym BH2 bend sym PH2 bend BHz wag PH, rock - BH, rockd BP str BHl rock PHl rockd PH2 wag
+
1.901 (1.899) 1.190 (1.190) 1.403 ( I ,402) 119.8 (1 19.7) 120.0 ( 120.3) 102.7 (102.7) 99.4 (99.5) 6.1 (6.0) 70.1 (70.0)
1.807 1.187 1.384 118.2 123.6 124.8 110.3
0.0 0.0
0.0 0.0 0.0 0.82 (0.85)
8.6 6.3 5.9 1.21
2794 (2780), A’’ 2698 (2687), A‘ 2584 (2573), A” 2576 (2567), A’ 1268 (1275), A’ 1222 (1215), A’ 1024 (1021), A‘ 964 (957), A” 746 (736), A’ 588 ( % I ) , A“ 554 (546), A’ 429 (424), A“
2824, B2 2715, A, 2724, B2 2696, AI 1254, A I 1162, A, 990, BI 889, BzC 827, AI 491, Bz‘ 497i, B, 723, A2
’
torsion OResults with the DZ + 2P + diff basis set are listed in parentheses; other results are obtained with the DZ + P basis set. Bond lengths are in A, angles are in deg, vibrational frequencies are in cm-’ for ‘IB, ”P, and ‘H isotopes, and dipole moments are in D. For C, symmetry, the molecular plane is taken as the y z plane (u,.’). bThe out-of-planeangle at B is defined as the angle between the BP axis and the HzB plane. That at P is the angle between the BP axis and the PHz plane. Energies are in kcal mol-’ relative to the nonplanar structure. Where motion of more than one internal coordinate makes a significant contribution to the normal mode, they are listed in order of decreasing importance. Plus and minus signs indicate relative phases. The rocking (asymmetric bending) motions are considered in phase if two H atoms move toward each other. For the planar molecule, the order of importance is reversed. Table 11. Properties of the Planar BH2PH- Anion’ ‘A’
r,(BP) ~SBHI) re(BH2) re(PHd UPBHI) ~e(PBH2) WPHd
proton affinity, SCFb proton affinity, C I S D ~ proton affinity, Davidson corb dipole moment‘ vibrational freq, u, asym BH str sym BH str PH str sym BH2 bend BPH bend - BH, rock BH2 wag BP str
torsion BPH bend
1.825 (1.829) 1.212 (1.210) 1.214 (1.212) 1.428 (1.424) 125.2 (124.5) 119.3 (1 19.1) 100.0 (1 00.3) 15.63 (15.37) 15.60 (15.25) 15.56 (15.18) 0.84 (0.64) 2564 (2563), A‘ 2527 (2525), A‘ 2396 (2391), A‘ 1269 (1 269), A‘ 977 (965), A‘ 956 (958), A“ 836 (815), A‘ 747 (718), A” 646 (647), A’
+ BHl rock + 2P + diff basis set are listed in parentheses; other results were obtained with the DZ + P basis set. See footnote in “Results with the DZ
Table I for units, etc. bThe proton affinity is the energy in eV relative to nonplanar BH,PH, with the same basis set.
