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第六章 P 区 元 素 PowerPoint PPT Presentation


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第六章 P 区 元 素. 硼烷 硼烷的命名 硼烷的结构分类和 Wade 规则 硼烷的拓扑结构 杂硼烷 金刚石 石墨 及其石墨 层间化合物 碳纤维 富勒烯 线型碳 纳米碳管 无机高分子. 习题 1 (1)(2)(4) , 2, 10, 11 (2) , 16, 18. 要点. 6.1 硼烷化学.

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第六章 P 区 元 素

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P

P


P

Wade

1(1)(2)(4),2, 10, 11(2), 16, 18


P

6.1

, B2H6B4H10B5H9, , BH4B3H8BnHn2(n612)


P

:

3NaBH4 4BF3 2B2H63NaBF4

6.1.1

6.1.1.1

1


P

NaBH4

H2SO4:

2NaBH4 2H2SO4 2NaHSO4B2H62H2

AlCl3, AlH2

:

B2O3 2Al 3H2 B2H6 Al2O3

, AlCl3


P

:

100, 10MPa

2B2H6 B4H10 H2

180

5B2H6 2B5H9 6H2

150,

2B2H6 B4H10 H2

,

110

K[B5H12] HClB5H11 H2 KCl

110

K[B6H11] HCl B6H12 KCl


P

(1) BH

BH

, BH,

373 K

2BH4 2B2H6 B6H62 7H2

2

:


P

(2)

B3H8

[(CH3)4N][B3H8][(CH3)3NBH3]

[(CH3)4N]2[B10H10] [CH3)4N]2[B12H12]

CsB3H8 Cs2B9H9 Cs2B10H10 Cs2B12H12

CsB3H8 Cs2B12H12

,


P

6.1.1.2

(B10H14, )

BnHn6(B4H10B5H11)BnHn4(B5H9423 KB10H14423 K443 KB10H16, 523 K)


P

(B2H6B5H9B10H14)

B10H14,

BnHn2


P

6.1.1.3

10,

, 10;

, ;

(),

: B5H11(11);

B10H14(14)


P

, ,

,

B12H122 -(2)

,

B12H122 -(2)


P

BnHn2(n612),

, -

1 (Closo)

6.2

:


P

H

H

H

H

H

H

H

(

B6H62)BH

, BH


P

2 ()(nido)

()BnHn4, -, (n1)-, ,

nido,


P

-, n4, n, 4B6H10, 10H6

H, 4H, 2B,


P

3 ()(arachno)

BnHn6,

B4H10B5H11B9H14

n2()

arachno,


P

H

B4H10B5H11B9H14

,, BH

BnHn6, n,

H


P

4 (hypho)

, , , , , ,


P

5 Wade

1971WadeWade(Wade.K.J.C.S. Chem, 1971, 292)

,


P

bn

bn1 BnHn2 BnHn2

(n)

bn2 BnHn4 BnHn4

() (n1)

bn3 BnHn6 BnHn6

(n2)

bn4 BnHn8 BnHn8

(n3)


P

2e

2e

2e

2e


P

[(CH)a(BH)pHq]c

qH(HH), c(SPN)n(nap)BHHCH, SPN433

, M:

M3a2pqc

b(3a2pqc)/2


P

1, BnHn2, (BH)n2, a0, q0, c2, pn, b(2n2)/2n1

2, B10H15, (BH)10H5, a0, q5, c1, p10, nap01010, b(21051)/213103,

3, B3C2H7, (CH)2(BH)3H2, a2, q2, c0, p3, nap235, b(32232)/2752, ()

-n(2)

-(1)

-(7)


P

4B10CPH11(CH)(BH)10Pa1q0c0p10Pnap(P)110112b(31210 3)/213121

5B11SH11(BH)11Sa0, q0c0p10Snap(S)011112b(211 4)/213121

-(11)

-(11)


P

6.3

6.3.1

, 2s22p1, 2s2p3, 4,


P

B2H6()

4

HB2H6

12

(2C2e), 4BH8, 4BH

BBH22sp32sp31


P

, 2sp31s: 3, , , 2, (3C2e)B2H6, 2

3C2e

, B2H6 2,

42C2eBH2


P

(1) , 2C2eBH

HB

BB, 3C2eB B

(2) BnHnm n B nH n 2C 2eBH s 3C2e t3C2e, y2C2eBB x 2C2e BH:

H B

B B(3C2e)B B(3C2e) BB(2C2e) BH(2C2e)

s t y x

B B

6.3.2

Lipscomb, (topological approach), :


P

styxBnHnmnm

nst

nB2C2e, n, n3e2e , B


P

msx

BnHnmnBnHnBHBH mBH(sx)HBH

nm/2styx

nBHn, mm/2, styx


P

, BnHnm

nst

msx

nm/2styx

(sx)(ty)

mty

nst

msx

nm/2ty m/2yx

nm/2(st)yxnyx

BnHnm,

, ,


P

H

H

1 B5H9

:B5H9(BH)5H4, n5, m4,b(524)/2752,

n5st

m4sx

m/24/22yx

H

H

s t y x

4 1 2 0

3 2 1 1

2 3 0 2

H

H

H

H

H

H

H

H

H

(9)

H

H

H

H

H

H

B B

B

B B

B B

B

B B

B B

B

B B

H

H

H

H

H

H

H

H

4120

3211

2302


P

H

B B

B

B B

H

B B

B

B B

B, , :

BB BH

3C2e 3C2e 2C2e 2C2e

B BB BB (2C2e)

BB (

)

(

)


P

BBH(BH)

, , ,


P

H

H

H

H

H

H

s t y x

6 1 3 0

5 0 2 1

4 1 1 2

3 2 0 3

H

H

H

2 B5H11

B5H11(BH)5H6, n5, m6,

b(526)/2853,

n5st

m6sx

m/26/23yx

(11)

t1

H

H

H

H

H

H

B B

B

B B

B B

B

B B

B B

B

B B

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

3203

5021

4112


P

H

H

H

H

H

H

H

H

H

H

s t y x

8 3 4 0

7 2 3 1

6 1 2 2

5 0 1 3

4 1 0 4

H

B B

B

B B

H

H

H

3 B5H13

B5H13(BH)5H8, n5, m8,

b(528)/2954,

(13)

5013

H

H

H

H

t

n5st

m8sx

m/28/24yx

H

H

B B

B

B B

H

H

H

H

H

H

4104


P

BnHnmc(BnHnm

cH)

ncst

mcsx

n(mc)/2c/2styx

(sx)(ty)

(mc)ty

nm/2cty

ncst

mcsx

nm/2cty

, ,

c


P

H

H

H

H

H

H

H

H

H

H

s t y x

4 0 2 3

3 1 1 4

2 2 0 5

H

H

H

4 B5H12

B5H12(BH)5H81, n5, m8 (: mc7, c1),

b(52811)/2954,

nc514st

mc817sx

nm/2c58/212ty

1

(1)

H

H

H

H

H

H

B B

B

B B

B B

B

B B

B B

B

B B

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

H

4023

3114

2205


P

6.3.3

-B6H62

B2pz2sspz(AO)spzH1sBHspzBspz, pxpyAO, ,

, B6spzAO12AO,

18AO


P

*

*

6AOMO,6MO:

a1g()t1u*()eg*();


P

12 AO MO

t2gt1ut2u*t1g*(,t2gt1u,t2u*t1g*)

*

t1g*

*

t2u*

t1g

t2u

t1g

t1u

t2g

t2g


P

t1u*()

s

pz

t2u*()

t1u

spz

eg*()

t2u

eg*

spzp

12AO

t1u*(*/)

t1u*

()

t1u(/*)

(HOMO)

t1u

t2g()

BH

6AO

a1g()

t2g

6BH

B6H62

a1g

B6H62


P

-AOt1u-AOt1u*,, t1u(/*)t1u*(*/)

B6H62266BH1214(a1g)2(t2g)6(t1u)67(61), t1ut1u*, B6H62

B6H62


P

H

H

2L2LBH3

()

H2B BH2

H2B BH2

2L[L2BH2][BH4]

()

H

H

1 Lewis

(1)

6.4


P

H

H

L

L

H2B BH3

H2B BH2

H

, L

H

L

2LBH3

()

H2B BH3

LLewis

L

H

L [L2BH2][BH4]()

H2B BH3

LLewis

L

Lewis


P

(2)

Lewis,

B5H92(CH3)3P B5H9[P(CH3)3]2

(3)

B10H14OH B10H13 H2O

B10H14H B10H13 H2

B10H14NH3 [NH4][B10H13]


P

2

B10H102 B12H122B10X102B12X122

3


P

, , H, ,

R,,Brown1957

1979


P

6.5

1 (Carboranes)

(CH)(BH)CHBH


P

nPr2O

nPr2O

,1, 2B10C2H12

B10H142Et2S [(C2H5)2S]2[B10H12]H2

[(C2H5)2S]2[B10H12]C2H2 B10C2H12 H2 2Et2S


P

,, ,

,,

,

(), , ,


P


P

CHH

()


P

,7, 8-C2B9H112, 21sp3, 512,6,

7,8-C2B9H112

2


P

,

,

[Fe(7,8-C2B9H11)2]2

C2B9H11MX


P

,

,

, 81, 7-C2B6H8

CoCl2

C5H5,9

(C2B6H8)Co(C5H5)

10C2B6H8[Co(C5H5)]2

1,7-C2B6H8

, :


P

BH2, ,

(1, 2-C2B9H11)Co(C5H5) (Co12)BH2, (Co)11(2, 4-C2B8H10)Co(C5H5)

(1,2-C2B9H11)CoIII(C5H5)


P

473 K1,5-C2B3H5Fe(CO)5(5-C5H5)Co(CO)2, , 5


P

6.6

6.6.1

21()


P

sp3

sp2

()s0.915p2.085(sp2.28)(3)1(s0.085p0.915) (p0.72);

sp

6.6.2


P

1


P

C() C()

rHm1.828 kJmol1

rGm2.796 kJmol1

rSm3.25 Jmol1K1

rGmrHmTrSm()

:


P

(298 K)

fGm0

fGm2.900 kJmol1

298 K100kPa

C()C() rGm2.900 kJmol1

rGm0

(3.515 gcm3)(2.260 gcm3)


P

G

Gp2Gp1V(p2p1)

p1100 kPaGp12.796 kJmol1p2, , Gp20 p2(Gp1/V) p1

p21.5109 Pa

1.5 GPa


P

298 K50100 GPa1 0002 000 , ,


P

310GPa1 0002 000

()


P

(CVD)

sp3sp3

()

CVD

(PCVD)


P

CVD PCVD


P


P

143pm

335 pm

669.6 pm

Csp2

CC143 pm335 pm

245.6pm

2


P

(GIC)


P

(GIC)


P

HClO4100 (OOH)


P


P

: 11C8K; 21C24K; 31C36K()15C8KK

(a)

(b)


P

, , , sp331CCCC, 730pm,


P

:


P

10100C8K90 K0.768 cm1285 K1.02 cm1

:

: (CF)nne nCnF

: nLi nLine

: nLi(CF)nnLiFnC

(3V)


P

(5.3107Sml)

()CF


P

C8KC8KHx(0x2), H2D2H2HT

C8K;

FeCl3 H2N2350 1 h90 %


P

Ni

-Fe2O3


P

3

()4


P


P

, ,

,


P

, , , , 3 000

, , (2 500m2g1), 3


P

1985SussexKrotoC6060C50C70C240C540

C60Buckminster Fuller(Fullerend)

C60

4


P

C603

C60C6020Kroto

1996

C60


P

C60

C28 C32

C50

2832506070240540

C70

C240

C540

C60


P

()C60122012

12


P

C601220533

0.7nm32,1.871022 cm31.34 nm

C60


P

C(F5)(F6)

(F)(V)(E)

FVE2

C3C2C

3V2E

2E5F56F6

C60V60

3V2EE90

2E5F56F6F6305F5/6

FVE2F5(305F5/6)60902

F512F620


P

C60s0.915p2.085()116CC138.8 pmCC143.2pmC70C240C540C60


P

C60C60


P

C60

1985C601990C60C60:


P

10g, , , C60C70, 90%C60C60C70

C60


P

573673 KC60C70


P

C60

C60, 400

C60C20C22

C6013C NMR143.2 C60


P

C60ps0.915p2.085

C60


P

C60:

(1)C60, 2-

(2) sp3


P

C60

1990C60C60

C60


P

C60: C60KRbCsHgTlBi; C60(KRb)

K3C60KC603KC601C6034K12

K3C60


P

VFeCoNiCuRhLaMxC60Ni(C60)2C60

C60C60

[email protected]


P

C60On(n5)

C60C60OC6018h7%C60O736, C60O (72016)C60OO


P

C60OsO4C60OsO4

C60OsO42C5H5N [Os(O)2(py)2(OC60O)]

C6H5CH3, 025


P

C60C60F2n(n1530)n30, C60C60Cl6C60Br8C60Br24

C60C60C60H2nnl18C60H60H/HC60C60H36


P

C60()

C60FSO3HSbF5H2SO4SO2ClF


P

C60 C60C60

CH3I

C6010 t-BuMgBr10CH3I C60(t-Bu)10Me10

()()C60

THF


P

C60

1825


P

C601.5 eV


P

TcIxC60Tc57 K

C540


P


P

C60C70C70


P

C60C60HIVP

C60


P

C6020 GPaC60C60C60


P


P

5

20501968Riss


P

spCarbyne () (CC)n , (CC)n --Carbyne (polymer)


P

3


P

0.1378 nm

0.1282 nm

0.1207nm

,

2 600 K6l03 MPa1- l -

-

-


P

CVD

, CVD


P

CuCl


P

, ,7, ,


P

, , , , , ,


P

Cl2411Cl; N2O4151

ReCCCCReReCCCCRe


P

, , -,


P

1991Iijima,,

6.3.3


P

(NTs)

()


P

(NTs)sp23246 pmCC142 pm

(MWNTs)(SWNTs)

ABAB250(0.34 nm)

(0.753) nm

1


P

, 1001 000, 1 00010 000,


P

10 mm30 mm6 mml04 Pa50 A20 V

Ni700


P

(1)

1005

(2)

(250

nm), ,


P

(3)


P

Y


P

PCM1

4585 ,


P

(4)


P

?

:


P

6.7

6.7.1

(1)

(2)

(3)

(4)


P

6.7.2

()


P

H

B C N O F

Al Si P S Cl

Ge As Se

Sn Sb Te

565


P

(1)

:

SSS

H H H

SiSiSi

H H H

:

PNPN

6.7.3


P

(2)

()


P

IUPAC

6.7.4


P

NbI4SeO2(NbI4)n(SeO2)nNbI4SeO2


P

6.7.5

1

(1)

S

SSS

S

300 5 min(S)nCS2S8

K[S]nK

I[S]nI


P

(2)

[SiH2]n

SiCl4SiBr410001100[SiH2]n[SiX2]n

(CH3)2SiCl2

n(CH3)2SiCl2 2nNa [(CH3)2Si] n 2nNaCl

20016hNaOH


P

(3)

S/NS4N4(SN)n

S4N4S2Cl2NH3

8D2d

,

S4N4

, , SN162 pm, (176 pm)SS(258 pm)SS

(208 pm)van der Waals(330 pm)


P

S4N4

S4N4

S4N4SN

VIAS4N4SN

22


P

I

I

I

0

I

I

I

I

I

2 6S2Cl216 NH3S4N4S812NH4Cl

(SN

)

S4N4

S2Cl2NH3S4N4


P

N2SS4N4?

S4N4SNSNSN400 kJmol1N2Ub(NN)945 kJmol1()S4N4S4N4N2SS4N4

, , N2S

S4N4


P

NSsp2,

NSNSNS120sp2

N, 1sp2S1sp2NSNpz

S, 1sp2N1sp2SN; S

pz

S4N412

NS?


P

S4N4

12SN1SN

S4N412


P

SSSSvan der WaalsS

SpzS3d(S3d)


P

S4N4300 S2N2S2N2(SN)n

(SN)n(SN)nvan der Waals(SN)nHgSm11000 Sm15 K5107Sm10.26 K

(SN)n, (SN)n


P

As4S4()S4N4


P

(4) ()

(PNCl2)n(n38)(PNCl2)3(PNCl2)4

Cl

N

P

(a) (PNCl2)3

(b) (PNCl2)4


P

Cl

N

P

(a) (PNCl2)3

(b) (PNCl2)4

sp2sp2Psp3PNNpzsp3PClPNd

[d(P)p(N)]


P

(dp)PX

[PNCl2]36NaOR [PN(OR)2]36NaCl


P

(PNCl2)3250350 , ()

n[PNCl2]3[PNCl2]3n

[PNCl2]3()[PNCl2]3Cl


P

Cl

[PNCl2]3


P

63 3030 18 kgcm2150300 %400 PCl

[PNCl2]n[PN(OH)2]n2nHCl nH3PO46NH3


P

57

, ,


P

{NP(OCH2CF3)[OCH2(CF2)3CF2H]}nPNFPNF(68 )SiO2MgOPNFPNF


P


P

BNBNCCBNBNCCBNCCB3N3H6()

C6H6

(B3N3H6)

2


P

B3N3H6

BB3N3H6HX (XClOHOR)

B3N3H63HX [H2NBHX]3

NH3B(OH)3


P

(B4N4H8)

C10H8(B5N5H8)


P

(1) ()

(2) ()

(3)

3


P

  • ()


  • P

    3


    P

    SiO2Al2O3l00200 500 CHN

    AXYM3A4A5A10X


    P

    A(6)8 --6812

    A


    P

    (420 pm)(220140 pm)


    P

    XY()()XYX

    Na86[(AlO2)86(SiO2)106]264H2O

    Y

    Na56[(AlO2)56 (SiO2)136]264H2O


    P

    YSi/AlXYXX

    Y


    P

    M

    Na8[(AlO2)8(SiO2)40]24H2O

    , 700 pm, 580pm, 660 pm, , 400 pm, 0.14 cm3g1


    P

    (KNaCa2)


    P

    (AlPO4)(AlPO4)n (n)AlO4PO4

    AlPO4()


    P

    (SAPO)(MAPO)(TAPO)AlPO4AlPO4


    P

    (ZrP)

    ZrPZrPTh()U()ZrP


    P

    ()


    P

    0.40.5 m


    P

    1

    (1) 1985C60( )

    (a)

    (b)

    (c)

    (d)

    (2) C60N60N60( )

    (a) N60

    (b) N60N2

    (c) 1molN601molN2


    P

    (d) N60N2

    (4) ( )

    (a) B2H6B4H10()

    (b)

    (c)

    (d)

    2 O2O22O2

    O2O2 O2

    O22


    P

    (1)

    (2) , ;

    (3)

    (4) , OO112121132149 pm,

    (5) 200490625 kJmol1

    (6)


    P

    O2O2 O2

    (7) F22

    10 1991Langmuir(BN)n

    (BN)n(Na2B4O7) 1 0731 273 K-(BN)n-(BN)n, -(BN)n, -(BN)n,

    (1)

    (2)

    (3) -(BN)n-(BN)n


    P

    11

    (1) pH3.85.4

    (2) (55 )Br2HCl

    (a)

    (b) HCl

    (c)


    P

    16

    18 B5H11


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