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STRUCTURE AND BONDING
• Organic compounds are compounds containing carbon • Carbon neither readily gives up nor readily accepts electrons
• Carbon shares electrons with other carbon atoms as well as with several different kinds of atoms
STRUCTURE OF THE ATOM AND ATOMIC ORBITALS
• atom consists of nucleus surrounded by electron cloud electron cloud nucleus • electrons housed in orbitals that are grouped in shells of increasing size and energy
• an atomic orbital can hold two electrons at most • a list of orbitals occupied by an atom’s electrons describes the atom’s ground-state electron configuration SB-2
ELECTRON CONFIGURATIONS OF SOME 2ND ROW ELEMENTS Atomic # 5 6 7 8 9 10 • use the following rules to assign electron configuration: Aufbau Principle: the lowest energy orbitals are filled first Pauli Exclusion Principle: a maximum of two spin paired electrons may be placed in each orbital Hund’s Rule: one electron is added to each degenerate (equal energy) orbital before a second electron is added The outermost shell is called the valence shell. SB-3 LEWIS STRUCTURES OF ATOMS • Lewis structures are concerned only with valence electrons • nucleus represented by symbol of element of interest • valence electrons represented by dots surrounding nucleus B C N O F Ne Atoms in the same group have the same number of valence electrons. The number of valence electrons is the same as the group number. SB-4 3 . Electrons in the valence shell are the ones involved in bonding.
e. or share electrons to achieve a noble gas electronic configuration SB-6 4 .g. For 2nd row elements.ELECTRON CONFIGURATIONS OF SOME 2ND ROW ELEMENTS Neon (a noble gas) has a full valence shell = 8 electrons (an octet). accept. SB-5 THE OCTET RULE Atoms form bonds to achieve a stable octet (noble gas configuration) exceptions to the octet rule. a valence shell octet = great stability.. P and S (may have “expanded octets”) Atoms can donate.
3.1. Alkane Alkene Alkyne Organic Nomenclature: McMurry 3. 2. 5. 4. 13.VALENCY Atoms in organic compounds form a fixed number of bonds. 6. 10.1.1 Extra help/practice available through SI workshop(s) SB-7 Which of the following line bond structures is correct? H H C H A H C C H H H C H B H C C H H C H H C C H H H C H C H C H C H D 1.2. Carbon can form one or more bonds to other carbon atoms. 4.4. A and B A and C B and D Only B Only C SB-8 5 .
d.THE NATURE OF CHEMICAL BONDS. A CLOSER LOOK AT ATOMIC STRUCTURE Quantum Mechanics • mathematical description of bonding that takes into account the wave nature of electrons • wave equation is solved to yield a series of wave functions (Ψ ) for the atom • wave functions may be positive. f. p. only s and p orbitals are important in organic chemistry • atomic orbital: region in space where the probability of finding an electron is large • s orbital • p orbitals SB-9 VALENCE BOND THEORY Example: Bonding in H2 • two atomic orbitals overlap • result is a σ-bond • all purely single bonds are σ-bonds SB-10 6 . negative or zero • Ψ describes a series of states with different energies for each electron • Ψ 2 gives the probability of finding an electron in a particular location in space • Heisenberg uncertainty principle: the position and momentum of an electron cannot simultaneously be known • plots of Ψ 2 in three dimensions generate electron “clouds” called orbitals • four types of orbitals: s.
BONDING IN CARBON COMPOUNDS ORBITAL HYBRIDIZATION • recall: carbon has a valency of four • cannot be adequately explained by ground-state electron configuration electron promotion orbital hybridization four hybrid sp3 orbitals • orbital hybridization is a mathematical combination of the 2s and 2p wave functions to obtain wave functions for the new sp3 orbitals • each sp3 orbital has ¼ s-character and ¾ p-character SB-11 THE STRUCTURE OF METHANE • the carbon of CH4 has four sp3 orbitals in a tetrahedral arrangement • an sp3 orbital looks like a p-orbital with one lobe greatly extended • each sp3 orbital overlaps with a 1s orbital of hydrogen ≡ ≡ • four identical C-H σ-bonds SB-12 7 .
VSEPR THEORY 3D Shape Virtually all molecules possess a 3-dimensional shape which is often not accurately represented by drawings Note that a dashed line indicates a bond is behind the page Note that a wedge indicates a bond is coming forward four bonds to carbon have tetrahedral arrangement One explanation is Valence Shell Electron Pair Repulsion (VSEPR) Electrons pairs want to be as far away from one another as possible SB-13 THE STRUCTURE OF ETHANE • each carbon forms σ-bonds to three hydrogens by overlap of C sp3 orbitals and H s orbitals • C-C σ-bond formed by end-to-end overlap of two sp3 orbitals • molecule is approximately tetrahedral around each carbon ≡ • because a σ-bond has cylindrical symmetry along the bond axis. there is relatively free rotation of groups joined by a single bond SB-14 8 .SHAPE OF ORGANIC COMPOUNDS.
bonds point toward corners of a regular triangle) • explained by orbital hybridization: electron promotion orbital hybridization three hybrid sp2 orbitals • hybridization of the 2s orbital and two 2p orbitals yields three sp2 hybrid orbitals • one 2p orbital remaining SB-15 THE STRUCTURE OF ETHENE • 2p orbital is perpendicular to plane of sp2 orbitals • sp2 orbitals used to form single (σ) bonds σ • 2p orbital used to form π-bond • combination of σ-bond and π-bond yields double bond typical of alkenes • note difference in C-C bond length for ethane compared to ethene SB-16 9 .THE STRUCTURE OF ETHENE • ethene (C2H4) contains a carbon-carbon double bond and is in the class of organic compounds called alkenes • the geometry around each carbon is called trigonal planar (all atoms in a single plane.
THE STRUCTURE OF ETHYNE • ethyne (C2H2) contains a carbon-carbon triple bond and is in the class of organic compounds called alkynes • the geometry around each carbon is linear with bond angles of 180° • explained by orbital hybridization: electron promotion orbital hybridization two hybrid sp orbitals • hybridization of the 2s orbital and one 2p orbital yields two sp hybrid orbitals • two 2p orbitals remaining SB-17 THE STRUCTURE OF ETHYNE • 2p orbitals are perpendicular to each other and to plane of sp orbitals • sp orbitals used to form single (σ) bonds σ • 2p orbitals used to form π-bonds • combination of σ-bond and two π-bonds yields triple bond typical of alkynes • note difference in C-C bond length for ethane compared to ethene compared to ethyne SB-18 10 .
2. s p sp sp2 sp3 SB-19 HYBRIDIZATION OF NITROGEN.What is the hybridization of the carbon atom in the following molecule? 1. PHOSPHORUS AND SULFUR • Nitrogen orbital hybridization four hybrid sp3 orbitals • nitrogen is sp3-hybridized with 1 e-pair → trigonal pyramidal SB-20 11 . 3. OXYGEN. 4. 5.
OXYGEN. PHOSPHORUS AND SULFUR • Oxygen orbital hybridization four hybrid sp3 orbitals • oxygen is sp3-hybridized with 2 e-pairs → bent SB-21 HYBRIDIZATION OF NITROGEN. PHOSPHORUS AND SULFUR • Phosphorus • phosphorus is sp3-hybridized with no e-pairs → tetrahedral • Sulfur • sulfur is sp3-hybridized with 2 e-pairs → bent SB-22 12 . OXYGEN.HYBRIDIZATION OF NITROGEN.
3. trigonal pyramidal SB-23 RELATIONSHIP BETWEEN HYBRIDIZATION AND VSEPR THEORY Hybridization Lone Pairs sp sp2 sp2 sp3 sp3 sp3 0 0 1 0 1 2 ~ Bond Angle 180° 120° 120° 109. 4. BF3. [Hint: BF3 readily accepts a pair of electrons to form a stable octet.5° 109. 2. trigonal pyramidal sp2.5° Molecular Geometry linear trigonal planar bent tetrahedral trigonal pyramidal bent SB-24 13 .] 1. sp3.5° 109. e.Given the ground state electronic configuration of boron. tetrahedral sp2.g. trigonal planar sp3. predict its hybridization state and geometry in its neutral compounds.
MOLECULAR ORBITAL (MO) THEORY • LCAO: mathematic operation by which wave functions are added or subtracted • number of MOs that result must always equal the number of AOs used SB-26 14 . ETHENE AND ETHYNE 110 pm sp3 (25% s-character) sp2 (33% s-character) sp (50% s-character) • C-C bond length decreases with increase in number of bonds • C-H bond length also decreases in the series bond length decreases with an increase in s-character of bond • 2s orbitals closer to the nucleus than 2p orbitals • hybridized orbital with more % s character closer to the nucleus than orbital with less s character SB-25 A SECOND PICTURE OF BONDING.BOND LENGTHS OF ETHANE.
MOLECULAR ORBITAL (MO) THEORY • σ-bonds can also be formed by end-to-end overlap of p-orbitals • σ-bonds can also be formed by end-to-end overlap of one s-orbital and one p-orbital Is there another way by which p-orbitals may overlap? SB-27 A SECOND PICTURE OF BONDING. MOLECULAR ORBITAL (MO) THEORY • “sideways” overlap of p-orbitals is also possible • result is a π-bond SB-28 15 .A SECOND PICTURE OF BONDING.
RELATIVE ENERGIES OF σ. The number of valence electrons is the same as the group number. SB-30 16 .AND π-ORBITALS • σ-bonding orbital is lower in energy than π-bonding orbital • lower energy = greater stability • σ-bonds are more difficult to break than π-bonds SB-29 LEWIS STRUCTURES OF ATOMS • Lewis structures are concerned only with valence electrons • nucleus represented by symbol of element of interest • valence electrons represented by dots surrounding nucleus B C N O F Ne Atoms in the same group have the same number of valence electrons.
DRAWING CHEMICAL STRUCTURES. H → 1 bond Answer: H C H C H H SB-32 17 . LEWIS STRUCTURES OF MOLECULES representation of a molecule showing electron pairs as a pair of dots or as a dash only valence electrons are indicated number of valence electrons is determined by position in periodic table (valence number = group number) 1 2 3 4 5 6 7 8 SB-31 LEWIS STRUCTURES OF MOLECULES drawing Lewis structures… Example: C2H4 determine total number of valence electrons required to satisfy octet rule for carbon and to provide each hydrogen with two electrons 2 x 8 + 4 x 2 = 24 determine total number of electrons available from valence shell of each atom 2 x 4 + 4 x 1 = 12 the difference represents the number of electrons that must be shared (12) the number of shared electrons / 2 = number of bonds required (6) Recall valency: C → 4 bonds.
.. O C 2- Note: 24 electrons available. O . F ... H → 1 bond. . Extra electrons are nonbonding electrons.O...... 8 used. .distribute to satisfy octet rule . F → 1 bond Answer: H H C H Note: 14 electrons available.. There are some exceptions that require “experience” SB-34 18 ..LEWIS STRUCTURES OF MOLECULES drawing Lewis structures… Try: CH3F determine total number of valence electrons required to satisfy octet rule for carbon and fluorine. .. distribute to satisfy octet rule SB-33 LEWIS STRUCTURES OF MOLECULES drawing Lewis structures… Try: CO32determine total number of valence electrons required to satisfy octet rule for carbon and oxygen 1 x 8 + 3 x 8 = 32 determine total number of electrons available from valence shell of each atom +/. and to provide each hydrogen with two electrons 2 x 8 + 3 x 2 = 22 determine total number of electrons available from valence shell of each atom 1 x 4 + 3 x 1 + 1 x 7 = 14 the difference represents the number of electrons that must be shared (8) the number of shared electrons / 2 = number of bonds required (4) Recall valency: C → 4 bonds. O → 2 bonds if neutral Answer: .. 6 remaining . 8 used.any existing charge 1 x 4 + 3 x 6 + 2 = 24 the difference represents the number of electrons that must be shared (8) the number of shared electrons / 2 = number of bonds required (4) Recall valency: C → 4 bonds. 16 remaining Extra electrons are nonbonding.
8 used. 24 remaining Extra electrons are nonbonding.distribute to satisfy octet rule 2- O O O S O O SB-35 REPRESENTATION OF STRUCTURAL FORMULAS Lewis structures • used to emphasize connectivity • relatively free rotation around single bonds SB-36 19 .any existing charge 1 x 6 + 4 x 6 + 2 = 32 the difference represents the number of electrons that must be shared (8) the number of shared electrons / 2 = number of bonds required (4) Answer: O X O S O 2- 2- Note: 32 electrons available.LEWIS STRUCTURES OF MOLECULES drawing Lewis structures… Try: SO42determine total number of valence electrons required to satisfy octet rule for sulfur and oxygen 1 x 8 + 4 x 8 = 40 determine total number of electrons available from valence shell of each atom +/.
REPRESENTATION OF STRUCTURAL FORMULAS Condensed structures SB-37 REPRESENTATION OF STRUCTURAL FORMULAS Bond-line structures SB-38 20 .
2.How many hydrogen atoms are present in the naturally-occurring terpene α-terpinene shown below? 1. 3. 5. 14 15 16 17 18 SB-39 REPRESENTATION OF STRUCTURAL FORMULAS 3-D Structures • used to emphasize tetrahedral arrangement at carbon SB-40 21 . 4.