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Mo Scheme of BF Fluorine Salcs and Boron Aos: S A ' (P, P) E' P A "

This document describes the molecular orbital scheme of the BF3 molecule. It discusses how the 2p orbitals on the fluorine atoms interact with the boron 2p orbitals to form sigma and pi bonding and antibonding molecular orbitals. Specifically, it outlines how the 2pz orbitals form out-of-plane pi interactions, the 2px orbitals form sigma bonds, and the 2py orbitals can form in-plane pi interactions. It also presents the complete molecular orbital diagram of BF3 and discusses how its lowest unoccupied molecular orbital allows it to behave as a Lewis acid by accepting an electron pair from a Lewis base like NH3.

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BRUNO RAMOS DE LIMA
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135 views8 pages

Mo Scheme of BF Fluorine Salcs and Boron Aos: S A ' (P, P) E' P A "

This document describes the molecular orbital scheme of the BF3 molecule. It discusses how the 2p orbitals on the fluorine atoms interact with the boron 2p orbitals to form sigma and pi bonding and antibonding molecular orbitals. Specifically, it outlines how the 2pz orbitals form out-of-plane pi interactions, the 2px orbitals form sigma bonds, and the 2py orbitals can form in-plane pi interactions. It also presents the complete molecular orbital diagram of BF3 and discusses how its lowest unoccupied molecular orbital allows it to behave as a Lewis acid by accepting an electron pair from a Lewis base like NH3.

Uploaded by

BRUNO RAMOS DE LIMA
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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MO Scheme of BF3

Fluorine SALCs and Boron AOs

! Assume that fluorine 2s orbitals are not involved in the


bonding and only consider the 2p orbitals.

! The 2pz orbital on each fluorine is perpendicular to the BF3


plane and capable of forming out-of-plane pi interactions
(ðz).

! The 2px orbital points toward the B atom and forms sigma
interactions (ó)

! The 2py orbital is parallel to the BF3 plane and has the
potential to form in-plane pi interactions (ð2).

The symmetries of the central boron AOs are as follows:

s = A1' (px, py) = E' pz = A2 "


Out-of-Plane Pi Interactions

! The effective pð interactions are the out-of-plane type


formed from combinations of 2pz AOs on both B and F
atoms.

! The formation of the SALCs is based on the following


vector set.

! The reducible representation and its decomposition are

D3h E 2C3 3C2 óh 2S3 3óv


Ãð 3 0 -1 -3 0 1

Ãð = A2" + E"

! The A2" SALC matches with the "empty" 2pz AO on B.

! The E" SALCs have no match on B and remain


nonbonding.
Pi-Only MO Scheme for BF3
SALCs for Core (Nonbonding) F 2s

D3h E 2C3 3C2 óh 2S3 3óv


Ã2s 3 0 1 3 0 1

Ã2s = A1' + E'


Sigma SALCs for F 2px

! The vector set of 2px sigma bonding is identical to the set


shown for 2s.
• Therefore, Ãó = A1' + E'.

! The A1' SALC matches with the boron 2s AO.

! The E' SALCs match with the degenerate boron 2px and 2py
AOs.
In-Plane Pi-SALCs

D3h E 2C3 3C2 óh 2S3 3óv


Ã2 3 0 -1 3 0 -1

Ã2 = A2' + E'

! The A2' SALC has no match in B AOs and must be strictly


nonbonding.

! The E' SALCs do match with boron 2px and 2py, which are
involved in sigma bonding.

! Assuming that the sigma interactions are more effective,


the in-plane pi interactions of the E' SALCs can be taken to
be essentially nonbonding.
Complete MO Scheme of BF3

The ordering of levels in the following complete MO scheme is


based on the P.E.S. data of G. H. King, et al.1

1
G. J. King, S. S. Krishnamurthy, M. F. Lappert, and J. B. Pedley, Faraday Disc. Chem.
Soc., 1972, 54, 70.
Lewis Acid Behavior of BF3
BF3 + NH3 ÷ F3B:NH3

! In terms of frontier orbital theory, the LUMO in BF3 is the


ð* 2a2" MO, which can receive an electron pair from a
Lewis base.
• This MO, formed from 2pz orbitals, is

Ö = c1ö(B) – c2[ö(Fa) + ö(Fb) + ö(Fc)]

• The LCAO for this is

! For the base NH3, the HOMO is the weakly bonding ó a1


MO (cf. MO scheme), which can provide electrons to the
boron ð* 2a2" MO in the following manner:

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