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    Chemistry of The Main Group Elements: Boron Through The Pnictogens

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    Pace Radit
    The document summarizes key information about several main group elements, including boron, carbon, nitrogen, silicon, and their compounds. It discusses their electron configurations, common oxidation states, bonding properties and reactivities. Specifically, it describes boron hydride clusters and their skeletal electron counting, carbon's ability to form multiple types of bonds and allotropes, nitrogen's role in important industrial processes like the Haber-Bosch process, and the structures and reactivities of small nitrogen-containing molecules.

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    Chemistry of The Main Group Elements: Boron Through The Pnictogens

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    Pace Radit
    51 views16 pages
    The document summarizes key information about several main group elements, including boron, carbon, nitrogen, silicon, and their compounds. It discusses their electron configurations, common oxidation states, bonding properties and reactivities. Specifically, it describes boron hydride clusters and their skeletal electron counting, carbon's ability to form multiple types of bonds and allotropes, nitrogen's role in important industrial processes like the Haber-Bosch process, and the structures and reactivities of small nitrogen-containing molecules.

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    Chemistry of boran

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    11-6

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    The document summarizes key information about several main group elements, including boron, carbon, nitrogen, silicon, and their compounds. It discusses their electron configurations, common oxidation states, bonding properties and reactivities. Specifically, it describes boron hydride clusters and their skeletal electron counting, carbon's ability to form multiple types of bonds and allotropes, nitrogen's role in important industrial processes like the Haber-Bosch process, and the structures and reactivities of small nitrogen-containing molecules.

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    © All Rights Reserved
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    51 views16 pages

    Chemistry of The Main Group Elements: Boron Through The Pnictogens

    Uploaded by

    Pace Radit
    The document summarizes key information about several main group elements, including boron, carbon, nitrogen, silicon, and their compounds. It discusses their electron configurations, common oxidation states, bonding properties and reactivities. Specifically, it describes boron hydride clusters and their skeletal electron counting, carbon's ability to form multiple types of bonds and allotropes, nitrogen's role in important industrial processes like the Haber-Bosch process, and the structures and reactivities of small nitrogen-containing molecules.

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    Chemistry of the Main Group

    Elements:
    Boron through the Pnictogens
    Sections 8.5-8.7 and 15.4.1

    Friday, November 6, 2015


    Group IIIA (13): B, Al, Ga, In, and Tl
    Diverse group of elements with three valence electrons
    • ns2p1 electron configuration
    • boron is a non-metal, all others in group are metals

    Group IIIA halide complexes


    • all members of the group react directly with halogens

    B12  18Cl2 
    12BCl3
    2Al 0  3Cl2 
     2AlCl3
    • the metals will also react with hydrohalic acids
    This idea goes
    2Al  6HCl 
    0
     2AlCl3  3H 2 back to the ∆Gf
    data for MH3

    • Group IIIA halides are Lewis acids, BX3 is hard, others are soft

    • reactivity
    AlCl3  3MeMgCl 
     AlMe3  3MgCl2

     Li BMe4  3LiCl
    BCl3  4MeLi 
    This result is completely
     B OH 3  3HCl
    BCl3  3H 2O  consistent with HSAB
    theory
    Boranes (Boron Hydride Clusters)
    The electron deficient nature of boron favors cluster formation

    Formula Skeletal e– Pairs Examples

    closo [BnHn]2– n+1 [B5H5]2– thru [B12H12]2–

    nido BnHn+4 n+2 B2H6, B5H9, B6H10

    arachno BnHn+6 n+3 B4H10, B5H11

    hypho BnHn+8 n+4 B8H16, B10H18, B14H22

    Skeletal Electron Counting


    • basic building block is BH unit that contains 4 electrons (3 from B and 1 from H)
    • two electrons are used in the B–H bond, leaving two electrons (a pair) for the cluster
    framework [B12H12]2–
    • each charge adds one electron, so does each extra H

    [B6H6]2– ⇒ 6 BH units B4H10 ⇒ 4 BH units


    6 × 4 = 24 BH electrons 4 × 4 = 16 BH electrons
    – 6 B–H = 12 B–H bonding electrons – 4 B–H = 8 B–H bonding electrons
    + 2e– for charge = 2 extra electrons + 6 H = 6 extra hydrogen electrons
    14 skeletal electrons 14 skeletal electrons
    Boron Hydride Clusters
    Closo boron hydride clusters are regular polygon shapes

    Nido and arachno boron hydride clusters are derived from the regular
    polyhedra with one or two vertices removed, respectively, and
    bridging hydrogen atoms added.

    Also see section 15.4.1


    Carbon
    Carbon is a remarkable element for its versatility as a building block
    • carbon forms double and triple bonds more readily than any other element
    • the tetrahedral, trigonal, and linear geometries of carbon provides access to a
    variety of different structures and allows for lots of structural complexity

    Carbon allotropes:

    diamond – 3D network of sp3


    carbon atoms connected by C–
    C single bonds
    graphite – stacks of 2D sheets
    of sp2 carbon atoms in fused
    six-membered rings

    fullerenes – geodesic
    spheres containing sp2
    carbons, C60, C70, C80, etc.
    carbon nanotubes – a
    graphene layer rolled up
    into a cylinder
    Carbon
    Carbon is a remarkable element for its versatility as a building block
    • carbon forms double and triple bonds more readily than any other element
    • the tetrahedral, trigonal, and linear geometries of carbon provides access to a
    variety of different structures and allows for lots of structural complexity

    Carbon allotropes:

    diamond – 3D network of sp3


    carbon atoms connected by C–
    C single bonds
    graphite – stacks of 2D sheets
    of sp2 carbon atoms in fused
    six-membered rings

    fullerenes – geodesic
    spheres containing sp2
    carbons, C60, C70, C80, etc.
    carbon nanotubes – a
    graphene layer rolled up
    into a cylinder
    Si, Ge, Sn, & Pb
    Heavier congeners of carbon have +2 and +4 oxidation states
    accessible
    Si s   2Cl2 g  
     Si IV Cl4 l 

    Sn s   Cl2 g  
     Sn II Cl2 s  
    2 
     Sn IV Cl4 l 
    Cl g

    mp 246 °C mp –33 °C

    Pb s   Cl2 g  
     Pb II Cl2 s  
    2 
    Cl g
     no reaction

    Inert pair effect – heavy p-block metals often ‘hold on’ to their ns2 valence
    electrons better than lighter p-block elements
    Group IVA (14) Geometries

    trigonal planar tetrahedral trigonal bipyramidal

    Notice that
    germanium has 12
    electrons around it.
    The octet rule can be
    violated for heavy p-
    square pyramidal block elements

    octahedral
    Multiple Bonding
    While multiple bonding is common for carbon, it is unusual for the
    heavier elements and often the species are only metastable

    Bulky substituents can prevent polymer formation and allow isolation


    of molecular compounds

    Mes = Mesitylene (1,3,5-trimethylbenzene)


    Multiple Bonding
    There is structural evidence for multiple bonding with heteroatoms
    • trisilylamines are planar

    • silylethers have large Si–O–Si angles


    • silanols form strong hydrogen bonds and are also stronger acids than the
    analogous alcohols

    We can explain this with pπ–dπ bonding

    • important to note that the strength of pπ–dπ bonding decreases as you go


    down the group because of worse orbital overlap
    Nitrogen
    Virtually all nitrogen compounds are derived from the Haber-Bosch
    process

    urea
    Nitrogen Oxides: NV
    Nitrate (NO3–) is an important industrial chemical prepared by a two-
    step process:
    kcal
    4NH 3 g   7O2 g  
     6H 2O l   4NO2 aq  G  97
    mol
    kcal
    3NO2 aq   H 2O l  
     2HNO3 aq   NO g  G  1.2
    mol

    Compare this to the direct oxidation of N2 by O2:

    kcal
    N 2 g   2O2 g  
     2NO2 g  G  12
    mol

    By first reducing the N2 with hydrogen, driving force is gained for the
    oxidation reaction in the formation of water as a byproduct
    Nitrogen Oxides: NII and NIV
    Nitrogen dioxide exists as an equilibrium mixture

    NO2 has further reactivity in water


    Nitrogen Oxides: NO
    “Molecule of the Year” in 1992

    Nobel Prize in Medicine in 1998 for many biological roles


    • neurotransmission
    • neuron-to-neuron signaling
    • vasodilator (heart disease)
    • relaxes smooth muscle tissue (endothelium-derived relaxing factor)
    Low-Valent Nitrogen Compounds

    0 +II –I +I –I
    Nitrous Oxide Azide

    –I
    –II –II
    –I

    Diazene
    Hydrazine

    Formal charge – electrons in bonds are evenly split


    between atoms (covalent perspective)

    Oxidation state – electrons in bonds get assigned to


    the more electronegative atom (ionic perspective)
    N2 + 4 H+ + 4 e–
    P, As, Sb, & Bi
    Moving down the group, the octet can again be expanded for P, As,
    and Sb...
    P4 s   6Cl2 g  
     4PCl3 l  
    4Cl2
     4PCl5 l  
    4Cl 
     4PCl6
    8 e– 10 e– 12 e–

    ...but the inert pair effect keeps bismuth from going past BiX3

    The halides are useful starting materials for further chemistry:

    phosphite

    phosphorimide

    phosphineamine

    phosphine imine

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