chapter 15 group 15 elementsmichael.lufaso/chem4612/chapter15.pdf13 nitrides: li 3n, na 3n, be 3n 2,...
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1
Chapter 15
Group 15 ElementsOccurrence and extraction
Physical Properties
Metals
Halides oxides hydroxides salts of oxoacids
Phosphoacids
Sulfides and selenides
2
httpwwwcpscgovPageFiles122137270pdf
Relative abundances of the group 15 elements in the Earthrsquos crust
The main components (by percentage volume) of the Earthrsquos atmosphere
httpwwwsemiconductor-todaycomnews_items2012APRILYOLE_170412html
3
Phosphorus containing nerve agents
Destruction of the nerve agents
Selected low-temperature baths involving liquid N2
4
covalent bond enthalpy terms (kJ mol1)
vs
5
Schematic representation of the electronic repulsion believed to weaken the FF bond in F2
N2 - dinitrogen
httpwwwbbccoukschoolsgcsebitesizescienceedexcel_pre_2011oneearthusefulproductsrev2shtml
Fractional distillation
httpwwwmvsenggcomproductsnitrogenmembranenitrogenmembrane_process_detail
Membrane separation
Composition of air
Methods to produce N2 on a small scale
6
tetrahedral P4
Part of one of the chain-like arrays of atoms present in the infinite lattice of Hittorfrsquosphosphorus
Part of one layer of puckered 6-membered rings present in black phosphorus
httpenwikipediaorgwikiFilePhosphCombyjpg
httpenwikipediaorgwikiFilePhosphorusAllotropessvg
Phosphorus
ArsenicArsenic antimony and bismuth in the solid state
Vapor phase
4M + 3O2 2M2O3 (M = As Sb Bi)
2As + 6NaOH 2Na3AsO3 + 3H2
7
httpwwwyettercocommedia-libraryvideospreview12jpg
8
Chemistry of ammonia (NH3)
barrier to inversion is low 24 kJ mol-1
4NH3 + 3O2 2N2 + 6H2
4NH3 + 5O2 ndashndashPtRh 4NO + 6H2O
NH3(aq) + H2O(l) [NH4]+(aq) + [OH]-(aq) Kb = 18x10-5
[NH4]+(aq) + H2O(l) [H3O]+(aq) + NH3(aq) Ka = 56x10-10
NH3 + HBr NH4Br
CaSO4 + 2NH3 + CO2 + H2O CaCO3 + [NH4]2SO4
NH3 + HNO3 NH4NO3
Oxidation products depend on conditions
Chemistry of phosphinephosphane (PH3)
K + PH3 K+ + [PH2]- + 12H2
HX + PH3 PH4X
[PH4]+ + H2O PH3 + [H3O]+
PH3 acts as a Lewis base forms a range of adducts
H3BmiddotPH3Cl3BmiddotPH3 Ni(PH3)4 Ni(PH3)2(CO)2
PH3 + 2O2 --Δ H3PO4
liquid NH3
9
Hydrides E2H4 (E = N P As)
(a) The structure of N2H4 and Newman projections showing (b) the observed gauche conformation and (c) the possible staggered conformation An eclipsed conformation is also possible
NH3 + NaOCl NH2Cl + NaOH fast
NH3 + NH2Cl + NaOH N2H4 + NaCl + H2O slow
Hydrazine (N2H4) is kinetically stable with respect to N2 and H2 ΔfH(298K) = +506 kJ mol-1
Removes O2 from industrial boilers (forms N2H4 + O2 N2 + 2H2O)
Alkyl derivatives used with N2O4 as rocket fuel
High Energy Density Materials
55-azotetrazolate dianion
[N2H5]2(2+) 2H2OBa2+ + [N2H5]2[SO4]
373 K in vacuo
ΔfH(s 298 K) = +858 kJmol(37 kJg)
[N2H5]2(2+)[N2H5]2
(2+) 2H2O
10
[P3H3]2-
Potential diagram for nitrogen at pH = 0
Latimer (or reduction potential diagrams) show the standard reduction potentials connecting various oxidation states of an element
Is hydroxlamine [NH3OH]+ stable with respect to disproportionation to N2 and [N2H5]+ amp [NH4]+
11
HN3
[N3]
[N3HN3]
[PPh4][N3] + Me3SiN3 + EtOH [PPh4][N3HN3] + Me3SiOEt
12
trans- [Ru(en)2(N2)(N3)] [Sn(N3)6]2-
Metal and non-metal azide compounds
N2 isolated 1790N3
- synthesized 1890N5
+ synthesized 1999
[N2F]+[SbF6] + HN3 [N5]+[SbF6]- + HF(i) Liquid HF 195 K(ii) Warm to 298 K
[N5]+[SbF6]-
[NO]+[SbF6]- + 25N2
[NO2]+[SbF6]- + 25N2
[Br2]+[SbF6]- + 25N2
NO
NO2
Br2
13
Nitrides
Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN
bullHydrolysis of saline hydrides liberates NH3
bullNa3N is hygroscopic
Na3N + 3H2O 3NaOH + NH3
bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities
Pernitrides [N2]2- are known for Sr Ba
bullConditions of 5600 bar of N2 at 920 K for BaN2
Si3N4 are used in glow plugs
titanium nitride coated saw blades
Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures
bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages
Phosphides
bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities
bull Group 1 metals form M3P and Group 2 metals form M3P2
bull Are hydrolyzed by water and can be considered ionic
httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract
14
Gallium Arsenide
bull Important group III-V semiconductor that crystallizes with zinc-blende structure
bull Band gap of 142 eV thus can be used to make devices that emit light in the infrared region
bull Exhibits high electron mobility 8500 cm2V-1s-1 vs silicon 1500 cm2V-1s-1
bull Disadvantages of GaAs vs Sibull Expensivebull Brittlebull Lower Thermal Conductivity
bull Highest-efficiency single-junction solar cell at 288
bull httpdxdoiorg1011092FPVSC20126317891
Unit cell of NiAs
Ni
As
NiAs (nickel arsenide)
15
[Sb8]2 or [Bi8]2 Pd-centered pentagonal antiprismatic structure of
[PdBi10]4
16
Selected reactions of PCl5
SbF54
[Sb2F11] [As6I8]2
17
[BiCl3(15-crown-5)] [BiCl3L]
Oxides of Nitrogen
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
2
httpwwwcpscgovPageFiles122137270pdf
Relative abundances of the group 15 elements in the Earthrsquos crust
The main components (by percentage volume) of the Earthrsquos atmosphere
httpwwwsemiconductor-todaycomnews_items2012APRILYOLE_170412html
3
Phosphorus containing nerve agents
Destruction of the nerve agents
Selected low-temperature baths involving liquid N2
4
covalent bond enthalpy terms (kJ mol1)
vs
5
Schematic representation of the electronic repulsion believed to weaken the FF bond in F2
N2 - dinitrogen
httpwwwbbccoukschoolsgcsebitesizescienceedexcel_pre_2011oneearthusefulproductsrev2shtml
Fractional distillation
httpwwwmvsenggcomproductsnitrogenmembranenitrogenmembrane_process_detail
Membrane separation
Composition of air
Methods to produce N2 on a small scale
6
tetrahedral P4
Part of one of the chain-like arrays of atoms present in the infinite lattice of Hittorfrsquosphosphorus
Part of one layer of puckered 6-membered rings present in black phosphorus
httpenwikipediaorgwikiFilePhosphCombyjpg
httpenwikipediaorgwikiFilePhosphorusAllotropessvg
Phosphorus
ArsenicArsenic antimony and bismuth in the solid state
Vapor phase
4M + 3O2 2M2O3 (M = As Sb Bi)
2As + 6NaOH 2Na3AsO3 + 3H2
7
httpwwwyettercocommedia-libraryvideospreview12jpg
8
Chemistry of ammonia (NH3)
barrier to inversion is low 24 kJ mol-1
4NH3 + 3O2 2N2 + 6H2
4NH3 + 5O2 ndashndashPtRh 4NO + 6H2O
NH3(aq) + H2O(l) [NH4]+(aq) + [OH]-(aq) Kb = 18x10-5
[NH4]+(aq) + H2O(l) [H3O]+(aq) + NH3(aq) Ka = 56x10-10
NH3 + HBr NH4Br
CaSO4 + 2NH3 + CO2 + H2O CaCO3 + [NH4]2SO4
NH3 + HNO3 NH4NO3
Oxidation products depend on conditions
Chemistry of phosphinephosphane (PH3)
K + PH3 K+ + [PH2]- + 12H2
HX + PH3 PH4X
[PH4]+ + H2O PH3 + [H3O]+
PH3 acts as a Lewis base forms a range of adducts
H3BmiddotPH3Cl3BmiddotPH3 Ni(PH3)4 Ni(PH3)2(CO)2
PH3 + 2O2 --Δ H3PO4
liquid NH3
9
Hydrides E2H4 (E = N P As)
(a) The structure of N2H4 and Newman projections showing (b) the observed gauche conformation and (c) the possible staggered conformation An eclipsed conformation is also possible
NH3 + NaOCl NH2Cl + NaOH fast
NH3 + NH2Cl + NaOH N2H4 + NaCl + H2O slow
Hydrazine (N2H4) is kinetically stable with respect to N2 and H2 ΔfH(298K) = +506 kJ mol-1
Removes O2 from industrial boilers (forms N2H4 + O2 N2 + 2H2O)
Alkyl derivatives used with N2O4 as rocket fuel
High Energy Density Materials
55-azotetrazolate dianion
[N2H5]2(2+) 2H2OBa2+ + [N2H5]2[SO4]
373 K in vacuo
ΔfH(s 298 K) = +858 kJmol(37 kJg)
[N2H5]2(2+)[N2H5]2
(2+) 2H2O
10
[P3H3]2-
Potential diagram for nitrogen at pH = 0
Latimer (or reduction potential diagrams) show the standard reduction potentials connecting various oxidation states of an element
Is hydroxlamine [NH3OH]+ stable with respect to disproportionation to N2 and [N2H5]+ amp [NH4]+
11
HN3
[N3]
[N3HN3]
[PPh4][N3] + Me3SiN3 + EtOH [PPh4][N3HN3] + Me3SiOEt
12
trans- [Ru(en)2(N2)(N3)] [Sn(N3)6]2-
Metal and non-metal azide compounds
N2 isolated 1790N3
- synthesized 1890N5
+ synthesized 1999
[N2F]+[SbF6] + HN3 [N5]+[SbF6]- + HF(i) Liquid HF 195 K(ii) Warm to 298 K
[N5]+[SbF6]-
[NO]+[SbF6]- + 25N2
[NO2]+[SbF6]- + 25N2
[Br2]+[SbF6]- + 25N2
NO
NO2
Br2
13
Nitrides
Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN
bullHydrolysis of saline hydrides liberates NH3
bullNa3N is hygroscopic
Na3N + 3H2O 3NaOH + NH3
bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities
Pernitrides [N2]2- are known for Sr Ba
bullConditions of 5600 bar of N2 at 920 K for BaN2
Si3N4 are used in glow plugs
titanium nitride coated saw blades
Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures
bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages
Phosphides
bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities
bull Group 1 metals form M3P and Group 2 metals form M3P2
bull Are hydrolyzed by water and can be considered ionic
httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract
14
Gallium Arsenide
bull Important group III-V semiconductor that crystallizes with zinc-blende structure
bull Band gap of 142 eV thus can be used to make devices that emit light in the infrared region
bull Exhibits high electron mobility 8500 cm2V-1s-1 vs silicon 1500 cm2V-1s-1
bull Disadvantages of GaAs vs Sibull Expensivebull Brittlebull Lower Thermal Conductivity
bull Highest-efficiency single-junction solar cell at 288
bull httpdxdoiorg1011092FPVSC20126317891
Unit cell of NiAs
Ni
As
NiAs (nickel arsenide)
15
[Sb8]2 or [Bi8]2 Pd-centered pentagonal antiprismatic structure of
[PdBi10]4
16
Selected reactions of PCl5
SbF54
[Sb2F11] [As6I8]2
17
[BiCl3(15-crown-5)] [BiCl3L]
Oxides of Nitrogen
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
3
Phosphorus containing nerve agents
Destruction of the nerve agents
Selected low-temperature baths involving liquid N2
4
covalent bond enthalpy terms (kJ mol1)
vs
5
Schematic representation of the electronic repulsion believed to weaken the FF bond in F2
N2 - dinitrogen
httpwwwbbccoukschoolsgcsebitesizescienceedexcel_pre_2011oneearthusefulproductsrev2shtml
Fractional distillation
httpwwwmvsenggcomproductsnitrogenmembranenitrogenmembrane_process_detail
Membrane separation
Composition of air
Methods to produce N2 on a small scale
6
tetrahedral P4
Part of one of the chain-like arrays of atoms present in the infinite lattice of Hittorfrsquosphosphorus
Part of one layer of puckered 6-membered rings present in black phosphorus
httpenwikipediaorgwikiFilePhosphCombyjpg
httpenwikipediaorgwikiFilePhosphorusAllotropessvg
Phosphorus
ArsenicArsenic antimony and bismuth in the solid state
Vapor phase
4M + 3O2 2M2O3 (M = As Sb Bi)
2As + 6NaOH 2Na3AsO3 + 3H2
7
httpwwwyettercocommedia-libraryvideospreview12jpg
8
Chemistry of ammonia (NH3)
barrier to inversion is low 24 kJ mol-1
4NH3 + 3O2 2N2 + 6H2
4NH3 + 5O2 ndashndashPtRh 4NO + 6H2O
NH3(aq) + H2O(l) [NH4]+(aq) + [OH]-(aq) Kb = 18x10-5
[NH4]+(aq) + H2O(l) [H3O]+(aq) + NH3(aq) Ka = 56x10-10
NH3 + HBr NH4Br
CaSO4 + 2NH3 + CO2 + H2O CaCO3 + [NH4]2SO4
NH3 + HNO3 NH4NO3
Oxidation products depend on conditions
Chemistry of phosphinephosphane (PH3)
K + PH3 K+ + [PH2]- + 12H2
HX + PH3 PH4X
[PH4]+ + H2O PH3 + [H3O]+
PH3 acts as a Lewis base forms a range of adducts
H3BmiddotPH3Cl3BmiddotPH3 Ni(PH3)4 Ni(PH3)2(CO)2
PH3 + 2O2 --Δ H3PO4
liquid NH3
9
Hydrides E2H4 (E = N P As)
(a) The structure of N2H4 and Newman projections showing (b) the observed gauche conformation and (c) the possible staggered conformation An eclipsed conformation is also possible
NH3 + NaOCl NH2Cl + NaOH fast
NH3 + NH2Cl + NaOH N2H4 + NaCl + H2O slow
Hydrazine (N2H4) is kinetically stable with respect to N2 and H2 ΔfH(298K) = +506 kJ mol-1
Removes O2 from industrial boilers (forms N2H4 + O2 N2 + 2H2O)
Alkyl derivatives used with N2O4 as rocket fuel
High Energy Density Materials
55-azotetrazolate dianion
[N2H5]2(2+) 2H2OBa2+ + [N2H5]2[SO4]
373 K in vacuo
ΔfH(s 298 K) = +858 kJmol(37 kJg)
[N2H5]2(2+)[N2H5]2
(2+) 2H2O
10
[P3H3]2-
Potential diagram for nitrogen at pH = 0
Latimer (or reduction potential diagrams) show the standard reduction potentials connecting various oxidation states of an element
Is hydroxlamine [NH3OH]+ stable with respect to disproportionation to N2 and [N2H5]+ amp [NH4]+
11
HN3
[N3]
[N3HN3]
[PPh4][N3] + Me3SiN3 + EtOH [PPh4][N3HN3] + Me3SiOEt
12
trans- [Ru(en)2(N2)(N3)] [Sn(N3)6]2-
Metal and non-metal azide compounds
N2 isolated 1790N3
- synthesized 1890N5
+ synthesized 1999
[N2F]+[SbF6] + HN3 [N5]+[SbF6]- + HF(i) Liquid HF 195 K(ii) Warm to 298 K
[N5]+[SbF6]-
[NO]+[SbF6]- + 25N2
[NO2]+[SbF6]- + 25N2
[Br2]+[SbF6]- + 25N2
NO
NO2
Br2
13
Nitrides
Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN
bullHydrolysis of saline hydrides liberates NH3
bullNa3N is hygroscopic
Na3N + 3H2O 3NaOH + NH3
bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities
Pernitrides [N2]2- are known for Sr Ba
bullConditions of 5600 bar of N2 at 920 K for BaN2
Si3N4 are used in glow plugs
titanium nitride coated saw blades
Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures
bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages
Phosphides
bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities
bull Group 1 metals form M3P and Group 2 metals form M3P2
bull Are hydrolyzed by water and can be considered ionic
httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract
14
Gallium Arsenide
bull Important group III-V semiconductor that crystallizes with zinc-blende structure
bull Band gap of 142 eV thus can be used to make devices that emit light in the infrared region
bull Exhibits high electron mobility 8500 cm2V-1s-1 vs silicon 1500 cm2V-1s-1
bull Disadvantages of GaAs vs Sibull Expensivebull Brittlebull Lower Thermal Conductivity
bull Highest-efficiency single-junction solar cell at 288
bull httpdxdoiorg1011092FPVSC20126317891
Unit cell of NiAs
Ni
As
NiAs (nickel arsenide)
15
[Sb8]2 or [Bi8]2 Pd-centered pentagonal antiprismatic structure of
[PdBi10]4
16
Selected reactions of PCl5
SbF54
[Sb2F11] [As6I8]2
17
[BiCl3(15-crown-5)] [BiCl3L]
Oxides of Nitrogen
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
4
covalent bond enthalpy terms (kJ mol1)
vs
5
Schematic representation of the electronic repulsion believed to weaken the FF bond in F2
N2 - dinitrogen
httpwwwbbccoukschoolsgcsebitesizescienceedexcel_pre_2011oneearthusefulproductsrev2shtml
Fractional distillation
httpwwwmvsenggcomproductsnitrogenmembranenitrogenmembrane_process_detail
Membrane separation
Composition of air
Methods to produce N2 on a small scale
6
tetrahedral P4
Part of one of the chain-like arrays of atoms present in the infinite lattice of Hittorfrsquosphosphorus
Part of one layer of puckered 6-membered rings present in black phosphorus
httpenwikipediaorgwikiFilePhosphCombyjpg
httpenwikipediaorgwikiFilePhosphorusAllotropessvg
Phosphorus
ArsenicArsenic antimony and bismuth in the solid state
Vapor phase
4M + 3O2 2M2O3 (M = As Sb Bi)
2As + 6NaOH 2Na3AsO3 + 3H2
7
httpwwwyettercocommedia-libraryvideospreview12jpg
8
Chemistry of ammonia (NH3)
barrier to inversion is low 24 kJ mol-1
4NH3 + 3O2 2N2 + 6H2
4NH3 + 5O2 ndashndashPtRh 4NO + 6H2O
NH3(aq) + H2O(l) [NH4]+(aq) + [OH]-(aq) Kb = 18x10-5
[NH4]+(aq) + H2O(l) [H3O]+(aq) + NH3(aq) Ka = 56x10-10
NH3 + HBr NH4Br
CaSO4 + 2NH3 + CO2 + H2O CaCO3 + [NH4]2SO4
NH3 + HNO3 NH4NO3
Oxidation products depend on conditions
Chemistry of phosphinephosphane (PH3)
K + PH3 K+ + [PH2]- + 12H2
HX + PH3 PH4X
[PH4]+ + H2O PH3 + [H3O]+
PH3 acts as a Lewis base forms a range of adducts
H3BmiddotPH3Cl3BmiddotPH3 Ni(PH3)4 Ni(PH3)2(CO)2
PH3 + 2O2 --Δ H3PO4
liquid NH3
9
Hydrides E2H4 (E = N P As)
(a) The structure of N2H4 and Newman projections showing (b) the observed gauche conformation and (c) the possible staggered conformation An eclipsed conformation is also possible
NH3 + NaOCl NH2Cl + NaOH fast
NH3 + NH2Cl + NaOH N2H4 + NaCl + H2O slow
Hydrazine (N2H4) is kinetically stable with respect to N2 and H2 ΔfH(298K) = +506 kJ mol-1
Removes O2 from industrial boilers (forms N2H4 + O2 N2 + 2H2O)
Alkyl derivatives used with N2O4 as rocket fuel
High Energy Density Materials
55-azotetrazolate dianion
[N2H5]2(2+) 2H2OBa2+ + [N2H5]2[SO4]
373 K in vacuo
ΔfH(s 298 K) = +858 kJmol(37 kJg)
[N2H5]2(2+)[N2H5]2
(2+) 2H2O
10
[P3H3]2-
Potential diagram for nitrogen at pH = 0
Latimer (or reduction potential diagrams) show the standard reduction potentials connecting various oxidation states of an element
Is hydroxlamine [NH3OH]+ stable with respect to disproportionation to N2 and [N2H5]+ amp [NH4]+
11
HN3
[N3]
[N3HN3]
[PPh4][N3] + Me3SiN3 + EtOH [PPh4][N3HN3] + Me3SiOEt
12
trans- [Ru(en)2(N2)(N3)] [Sn(N3)6]2-
Metal and non-metal azide compounds
N2 isolated 1790N3
- synthesized 1890N5
+ synthesized 1999
[N2F]+[SbF6] + HN3 [N5]+[SbF6]- + HF(i) Liquid HF 195 K(ii) Warm to 298 K
[N5]+[SbF6]-
[NO]+[SbF6]- + 25N2
[NO2]+[SbF6]- + 25N2
[Br2]+[SbF6]- + 25N2
NO
NO2
Br2
13
Nitrides
Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN
bullHydrolysis of saline hydrides liberates NH3
bullNa3N is hygroscopic
Na3N + 3H2O 3NaOH + NH3
bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities
Pernitrides [N2]2- are known for Sr Ba
bullConditions of 5600 bar of N2 at 920 K for BaN2
Si3N4 are used in glow plugs
titanium nitride coated saw blades
Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures
bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages
Phosphides
bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities
bull Group 1 metals form M3P and Group 2 metals form M3P2
bull Are hydrolyzed by water and can be considered ionic
httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract
14
Gallium Arsenide
bull Important group III-V semiconductor that crystallizes with zinc-blende structure
bull Band gap of 142 eV thus can be used to make devices that emit light in the infrared region
bull Exhibits high electron mobility 8500 cm2V-1s-1 vs silicon 1500 cm2V-1s-1
bull Disadvantages of GaAs vs Sibull Expensivebull Brittlebull Lower Thermal Conductivity
bull Highest-efficiency single-junction solar cell at 288
bull httpdxdoiorg1011092FPVSC20126317891
Unit cell of NiAs
Ni
As
NiAs (nickel arsenide)
15
[Sb8]2 or [Bi8]2 Pd-centered pentagonal antiprismatic structure of
[PdBi10]4
16
Selected reactions of PCl5
SbF54
[Sb2F11] [As6I8]2
17
[BiCl3(15-crown-5)] [BiCl3L]
Oxides of Nitrogen
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
5
Schematic representation of the electronic repulsion believed to weaken the FF bond in F2
N2 - dinitrogen
httpwwwbbccoukschoolsgcsebitesizescienceedexcel_pre_2011oneearthusefulproductsrev2shtml
Fractional distillation
httpwwwmvsenggcomproductsnitrogenmembranenitrogenmembrane_process_detail
Membrane separation
Composition of air
Methods to produce N2 on a small scale
6
tetrahedral P4
Part of one of the chain-like arrays of atoms present in the infinite lattice of Hittorfrsquosphosphorus
Part of one layer of puckered 6-membered rings present in black phosphorus
httpenwikipediaorgwikiFilePhosphCombyjpg
httpenwikipediaorgwikiFilePhosphorusAllotropessvg
Phosphorus
ArsenicArsenic antimony and bismuth in the solid state
Vapor phase
4M + 3O2 2M2O3 (M = As Sb Bi)
2As + 6NaOH 2Na3AsO3 + 3H2
7
httpwwwyettercocommedia-libraryvideospreview12jpg
8
Chemistry of ammonia (NH3)
barrier to inversion is low 24 kJ mol-1
4NH3 + 3O2 2N2 + 6H2
4NH3 + 5O2 ndashndashPtRh 4NO + 6H2O
NH3(aq) + H2O(l) [NH4]+(aq) + [OH]-(aq) Kb = 18x10-5
[NH4]+(aq) + H2O(l) [H3O]+(aq) + NH3(aq) Ka = 56x10-10
NH3 + HBr NH4Br
CaSO4 + 2NH3 + CO2 + H2O CaCO3 + [NH4]2SO4
NH3 + HNO3 NH4NO3
Oxidation products depend on conditions
Chemistry of phosphinephosphane (PH3)
K + PH3 K+ + [PH2]- + 12H2
HX + PH3 PH4X
[PH4]+ + H2O PH3 + [H3O]+
PH3 acts as a Lewis base forms a range of adducts
H3BmiddotPH3Cl3BmiddotPH3 Ni(PH3)4 Ni(PH3)2(CO)2
PH3 + 2O2 --Δ H3PO4
liquid NH3
9
Hydrides E2H4 (E = N P As)
(a) The structure of N2H4 and Newman projections showing (b) the observed gauche conformation and (c) the possible staggered conformation An eclipsed conformation is also possible
NH3 + NaOCl NH2Cl + NaOH fast
NH3 + NH2Cl + NaOH N2H4 + NaCl + H2O slow
Hydrazine (N2H4) is kinetically stable with respect to N2 and H2 ΔfH(298K) = +506 kJ mol-1
Removes O2 from industrial boilers (forms N2H4 + O2 N2 + 2H2O)
Alkyl derivatives used with N2O4 as rocket fuel
High Energy Density Materials
55-azotetrazolate dianion
[N2H5]2(2+) 2H2OBa2+ + [N2H5]2[SO4]
373 K in vacuo
ΔfH(s 298 K) = +858 kJmol(37 kJg)
[N2H5]2(2+)[N2H5]2
(2+) 2H2O
10
[P3H3]2-
Potential diagram for nitrogen at pH = 0
Latimer (or reduction potential diagrams) show the standard reduction potentials connecting various oxidation states of an element
Is hydroxlamine [NH3OH]+ stable with respect to disproportionation to N2 and [N2H5]+ amp [NH4]+
11
HN3
[N3]
[N3HN3]
[PPh4][N3] + Me3SiN3 + EtOH [PPh4][N3HN3] + Me3SiOEt
12
trans- [Ru(en)2(N2)(N3)] [Sn(N3)6]2-
Metal and non-metal azide compounds
N2 isolated 1790N3
- synthesized 1890N5
+ synthesized 1999
[N2F]+[SbF6] + HN3 [N5]+[SbF6]- + HF(i) Liquid HF 195 K(ii) Warm to 298 K
[N5]+[SbF6]-
[NO]+[SbF6]- + 25N2
[NO2]+[SbF6]- + 25N2
[Br2]+[SbF6]- + 25N2
NO
NO2
Br2
13
Nitrides
Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN
bullHydrolysis of saline hydrides liberates NH3
bullNa3N is hygroscopic
Na3N + 3H2O 3NaOH + NH3
bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities
Pernitrides [N2]2- are known for Sr Ba
bullConditions of 5600 bar of N2 at 920 K for BaN2
Si3N4 are used in glow plugs
titanium nitride coated saw blades
Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures
bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages
Phosphides
bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities
bull Group 1 metals form M3P and Group 2 metals form M3P2
bull Are hydrolyzed by water and can be considered ionic
httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract
14
Gallium Arsenide
bull Important group III-V semiconductor that crystallizes with zinc-blende structure
bull Band gap of 142 eV thus can be used to make devices that emit light in the infrared region
bull Exhibits high electron mobility 8500 cm2V-1s-1 vs silicon 1500 cm2V-1s-1
bull Disadvantages of GaAs vs Sibull Expensivebull Brittlebull Lower Thermal Conductivity
bull Highest-efficiency single-junction solar cell at 288
bull httpdxdoiorg1011092FPVSC20126317891
Unit cell of NiAs
Ni
As
NiAs (nickel arsenide)
15
[Sb8]2 or [Bi8]2 Pd-centered pentagonal antiprismatic structure of
[PdBi10]4
16
Selected reactions of PCl5
SbF54
[Sb2F11] [As6I8]2
17
[BiCl3(15-crown-5)] [BiCl3L]
Oxides of Nitrogen
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
6
tetrahedral P4
Part of one of the chain-like arrays of atoms present in the infinite lattice of Hittorfrsquosphosphorus
Part of one layer of puckered 6-membered rings present in black phosphorus
httpenwikipediaorgwikiFilePhosphCombyjpg
httpenwikipediaorgwikiFilePhosphorusAllotropessvg
Phosphorus
ArsenicArsenic antimony and bismuth in the solid state
Vapor phase
4M + 3O2 2M2O3 (M = As Sb Bi)
2As + 6NaOH 2Na3AsO3 + 3H2
7
httpwwwyettercocommedia-libraryvideospreview12jpg
8
Chemistry of ammonia (NH3)
barrier to inversion is low 24 kJ mol-1
4NH3 + 3O2 2N2 + 6H2
4NH3 + 5O2 ndashndashPtRh 4NO + 6H2O
NH3(aq) + H2O(l) [NH4]+(aq) + [OH]-(aq) Kb = 18x10-5
[NH4]+(aq) + H2O(l) [H3O]+(aq) + NH3(aq) Ka = 56x10-10
NH3 + HBr NH4Br
CaSO4 + 2NH3 + CO2 + H2O CaCO3 + [NH4]2SO4
NH3 + HNO3 NH4NO3
Oxidation products depend on conditions
Chemistry of phosphinephosphane (PH3)
K + PH3 K+ + [PH2]- + 12H2
HX + PH3 PH4X
[PH4]+ + H2O PH3 + [H3O]+
PH3 acts as a Lewis base forms a range of adducts
H3BmiddotPH3Cl3BmiddotPH3 Ni(PH3)4 Ni(PH3)2(CO)2
PH3 + 2O2 --Δ H3PO4
liquid NH3
9
Hydrides E2H4 (E = N P As)
(a) The structure of N2H4 and Newman projections showing (b) the observed gauche conformation and (c) the possible staggered conformation An eclipsed conformation is also possible
NH3 + NaOCl NH2Cl + NaOH fast
NH3 + NH2Cl + NaOH N2H4 + NaCl + H2O slow
Hydrazine (N2H4) is kinetically stable with respect to N2 and H2 ΔfH(298K) = +506 kJ mol-1
Removes O2 from industrial boilers (forms N2H4 + O2 N2 + 2H2O)
Alkyl derivatives used with N2O4 as rocket fuel
High Energy Density Materials
55-azotetrazolate dianion
[N2H5]2(2+) 2H2OBa2+ + [N2H5]2[SO4]
373 K in vacuo
ΔfH(s 298 K) = +858 kJmol(37 kJg)
[N2H5]2(2+)[N2H5]2
(2+) 2H2O
10
[P3H3]2-
Potential diagram for nitrogen at pH = 0
Latimer (or reduction potential diagrams) show the standard reduction potentials connecting various oxidation states of an element
Is hydroxlamine [NH3OH]+ stable with respect to disproportionation to N2 and [N2H5]+ amp [NH4]+
11
HN3
[N3]
[N3HN3]
[PPh4][N3] + Me3SiN3 + EtOH [PPh4][N3HN3] + Me3SiOEt
12
trans- [Ru(en)2(N2)(N3)] [Sn(N3)6]2-
Metal and non-metal azide compounds
N2 isolated 1790N3
- synthesized 1890N5
+ synthesized 1999
[N2F]+[SbF6] + HN3 [N5]+[SbF6]- + HF(i) Liquid HF 195 K(ii) Warm to 298 K
[N5]+[SbF6]-
[NO]+[SbF6]- + 25N2
[NO2]+[SbF6]- + 25N2
[Br2]+[SbF6]- + 25N2
NO
NO2
Br2
13
Nitrides
Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN
bullHydrolysis of saline hydrides liberates NH3
bullNa3N is hygroscopic
Na3N + 3H2O 3NaOH + NH3
bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities
Pernitrides [N2]2- are known for Sr Ba
bullConditions of 5600 bar of N2 at 920 K for BaN2
Si3N4 are used in glow plugs
titanium nitride coated saw blades
Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures
bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages
Phosphides
bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities
bull Group 1 metals form M3P and Group 2 metals form M3P2
bull Are hydrolyzed by water and can be considered ionic
httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract
14
Gallium Arsenide
bull Important group III-V semiconductor that crystallizes with zinc-blende structure
bull Band gap of 142 eV thus can be used to make devices that emit light in the infrared region
bull Exhibits high electron mobility 8500 cm2V-1s-1 vs silicon 1500 cm2V-1s-1
bull Disadvantages of GaAs vs Sibull Expensivebull Brittlebull Lower Thermal Conductivity
bull Highest-efficiency single-junction solar cell at 288
bull httpdxdoiorg1011092FPVSC20126317891
Unit cell of NiAs
Ni
As
NiAs (nickel arsenide)
15
[Sb8]2 or [Bi8]2 Pd-centered pentagonal antiprismatic structure of
[PdBi10]4
16
Selected reactions of PCl5
SbF54
[Sb2F11] [As6I8]2
17
[BiCl3(15-crown-5)] [BiCl3L]
Oxides of Nitrogen
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
7
httpwwwyettercocommedia-libraryvideospreview12jpg
8
Chemistry of ammonia (NH3)
barrier to inversion is low 24 kJ mol-1
4NH3 + 3O2 2N2 + 6H2
4NH3 + 5O2 ndashndashPtRh 4NO + 6H2O
NH3(aq) + H2O(l) [NH4]+(aq) + [OH]-(aq) Kb = 18x10-5
[NH4]+(aq) + H2O(l) [H3O]+(aq) + NH3(aq) Ka = 56x10-10
NH3 + HBr NH4Br
CaSO4 + 2NH3 + CO2 + H2O CaCO3 + [NH4]2SO4
NH3 + HNO3 NH4NO3
Oxidation products depend on conditions
Chemistry of phosphinephosphane (PH3)
K + PH3 K+ + [PH2]- + 12H2
HX + PH3 PH4X
[PH4]+ + H2O PH3 + [H3O]+
PH3 acts as a Lewis base forms a range of adducts
H3BmiddotPH3Cl3BmiddotPH3 Ni(PH3)4 Ni(PH3)2(CO)2
PH3 + 2O2 --Δ H3PO4
liquid NH3
9
Hydrides E2H4 (E = N P As)
(a) The structure of N2H4 and Newman projections showing (b) the observed gauche conformation and (c) the possible staggered conformation An eclipsed conformation is also possible
NH3 + NaOCl NH2Cl + NaOH fast
NH3 + NH2Cl + NaOH N2H4 + NaCl + H2O slow
Hydrazine (N2H4) is kinetically stable with respect to N2 and H2 ΔfH(298K) = +506 kJ mol-1
Removes O2 from industrial boilers (forms N2H4 + O2 N2 + 2H2O)
Alkyl derivatives used with N2O4 as rocket fuel
High Energy Density Materials
55-azotetrazolate dianion
[N2H5]2(2+) 2H2OBa2+ + [N2H5]2[SO4]
373 K in vacuo
ΔfH(s 298 K) = +858 kJmol(37 kJg)
[N2H5]2(2+)[N2H5]2
(2+) 2H2O
10
[P3H3]2-
Potential diagram for nitrogen at pH = 0
Latimer (or reduction potential diagrams) show the standard reduction potentials connecting various oxidation states of an element
Is hydroxlamine [NH3OH]+ stable with respect to disproportionation to N2 and [N2H5]+ amp [NH4]+
11
HN3
[N3]
[N3HN3]
[PPh4][N3] + Me3SiN3 + EtOH [PPh4][N3HN3] + Me3SiOEt
12
trans- [Ru(en)2(N2)(N3)] [Sn(N3)6]2-
Metal and non-metal azide compounds
N2 isolated 1790N3
- synthesized 1890N5
+ synthesized 1999
[N2F]+[SbF6] + HN3 [N5]+[SbF6]- + HF(i) Liquid HF 195 K(ii) Warm to 298 K
[N5]+[SbF6]-
[NO]+[SbF6]- + 25N2
[NO2]+[SbF6]- + 25N2
[Br2]+[SbF6]- + 25N2
NO
NO2
Br2
13
Nitrides
Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN
bullHydrolysis of saline hydrides liberates NH3
bullNa3N is hygroscopic
Na3N + 3H2O 3NaOH + NH3
bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities
Pernitrides [N2]2- are known for Sr Ba
bullConditions of 5600 bar of N2 at 920 K for BaN2
Si3N4 are used in glow plugs
titanium nitride coated saw blades
Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures
bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages
Phosphides
bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities
bull Group 1 metals form M3P and Group 2 metals form M3P2
bull Are hydrolyzed by water and can be considered ionic
httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract
14
Gallium Arsenide
bull Important group III-V semiconductor that crystallizes with zinc-blende structure
bull Band gap of 142 eV thus can be used to make devices that emit light in the infrared region
bull Exhibits high electron mobility 8500 cm2V-1s-1 vs silicon 1500 cm2V-1s-1
bull Disadvantages of GaAs vs Sibull Expensivebull Brittlebull Lower Thermal Conductivity
bull Highest-efficiency single-junction solar cell at 288
bull httpdxdoiorg1011092FPVSC20126317891
Unit cell of NiAs
Ni
As
NiAs (nickel arsenide)
15
[Sb8]2 or [Bi8]2 Pd-centered pentagonal antiprismatic structure of
[PdBi10]4
16
Selected reactions of PCl5
SbF54
[Sb2F11] [As6I8]2
17
[BiCl3(15-crown-5)] [BiCl3L]
Oxides of Nitrogen
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
8
Chemistry of ammonia (NH3)
barrier to inversion is low 24 kJ mol-1
4NH3 + 3O2 2N2 + 6H2
4NH3 + 5O2 ndashndashPtRh 4NO + 6H2O
NH3(aq) + H2O(l) [NH4]+(aq) + [OH]-(aq) Kb = 18x10-5
[NH4]+(aq) + H2O(l) [H3O]+(aq) + NH3(aq) Ka = 56x10-10
NH3 + HBr NH4Br
CaSO4 + 2NH3 + CO2 + H2O CaCO3 + [NH4]2SO4
NH3 + HNO3 NH4NO3
Oxidation products depend on conditions
Chemistry of phosphinephosphane (PH3)
K + PH3 K+ + [PH2]- + 12H2
HX + PH3 PH4X
[PH4]+ + H2O PH3 + [H3O]+
PH3 acts as a Lewis base forms a range of adducts
H3BmiddotPH3Cl3BmiddotPH3 Ni(PH3)4 Ni(PH3)2(CO)2
PH3 + 2O2 --Δ H3PO4
liquid NH3
9
Hydrides E2H4 (E = N P As)
(a) The structure of N2H4 and Newman projections showing (b) the observed gauche conformation and (c) the possible staggered conformation An eclipsed conformation is also possible
NH3 + NaOCl NH2Cl + NaOH fast
NH3 + NH2Cl + NaOH N2H4 + NaCl + H2O slow
Hydrazine (N2H4) is kinetically stable with respect to N2 and H2 ΔfH(298K) = +506 kJ mol-1
Removes O2 from industrial boilers (forms N2H4 + O2 N2 + 2H2O)
Alkyl derivatives used with N2O4 as rocket fuel
High Energy Density Materials
55-azotetrazolate dianion
[N2H5]2(2+) 2H2OBa2+ + [N2H5]2[SO4]
373 K in vacuo
ΔfH(s 298 K) = +858 kJmol(37 kJg)
[N2H5]2(2+)[N2H5]2
(2+) 2H2O
10
[P3H3]2-
Potential diagram for nitrogen at pH = 0
Latimer (or reduction potential diagrams) show the standard reduction potentials connecting various oxidation states of an element
Is hydroxlamine [NH3OH]+ stable with respect to disproportionation to N2 and [N2H5]+ amp [NH4]+
11
HN3
[N3]
[N3HN3]
[PPh4][N3] + Me3SiN3 + EtOH [PPh4][N3HN3] + Me3SiOEt
12
trans- [Ru(en)2(N2)(N3)] [Sn(N3)6]2-
Metal and non-metal azide compounds
N2 isolated 1790N3
- synthesized 1890N5
+ synthesized 1999
[N2F]+[SbF6] + HN3 [N5]+[SbF6]- + HF(i) Liquid HF 195 K(ii) Warm to 298 K
[N5]+[SbF6]-
[NO]+[SbF6]- + 25N2
[NO2]+[SbF6]- + 25N2
[Br2]+[SbF6]- + 25N2
NO
NO2
Br2
13
Nitrides
Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN
bullHydrolysis of saline hydrides liberates NH3
bullNa3N is hygroscopic
Na3N + 3H2O 3NaOH + NH3
bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities
Pernitrides [N2]2- are known for Sr Ba
bullConditions of 5600 bar of N2 at 920 K for BaN2
Si3N4 are used in glow plugs
titanium nitride coated saw blades
Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures
bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages
Phosphides
bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities
bull Group 1 metals form M3P and Group 2 metals form M3P2
bull Are hydrolyzed by water and can be considered ionic
httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract
14
Gallium Arsenide
bull Important group III-V semiconductor that crystallizes with zinc-blende structure
bull Band gap of 142 eV thus can be used to make devices that emit light in the infrared region
bull Exhibits high electron mobility 8500 cm2V-1s-1 vs silicon 1500 cm2V-1s-1
bull Disadvantages of GaAs vs Sibull Expensivebull Brittlebull Lower Thermal Conductivity
bull Highest-efficiency single-junction solar cell at 288
bull httpdxdoiorg1011092FPVSC20126317891
Unit cell of NiAs
Ni
As
NiAs (nickel arsenide)
15
[Sb8]2 or [Bi8]2 Pd-centered pentagonal antiprismatic structure of
[PdBi10]4
16
Selected reactions of PCl5
SbF54
[Sb2F11] [As6I8]2
17
[BiCl3(15-crown-5)] [BiCl3L]
Oxides of Nitrogen
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
9
Hydrides E2H4 (E = N P As)
(a) The structure of N2H4 and Newman projections showing (b) the observed gauche conformation and (c) the possible staggered conformation An eclipsed conformation is also possible
NH3 + NaOCl NH2Cl + NaOH fast
NH3 + NH2Cl + NaOH N2H4 + NaCl + H2O slow
Hydrazine (N2H4) is kinetically stable with respect to N2 and H2 ΔfH(298K) = +506 kJ mol-1
Removes O2 from industrial boilers (forms N2H4 + O2 N2 + 2H2O)
Alkyl derivatives used with N2O4 as rocket fuel
High Energy Density Materials
55-azotetrazolate dianion
[N2H5]2(2+) 2H2OBa2+ + [N2H5]2[SO4]
373 K in vacuo
ΔfH(s 298 K) = +858 kJmol(37 kJg)
[N2H5]2(2+)[N2H5]2
(2+) 2H2O
10
[P3H3]2-
Potential diagram for nitrogen at pH = 0
Latimer (or reduction potential diagrams) show the standard reduction potentials connecting various oxidation states of an element
Is hydroxlamine [NH3OH]+ stable with respect to disproportionation to N2 and [N2H5]+ amp [NH4]+
11
HN3
[N3]
[N3HN3]
[PPh4][N3] + Me3SiN3 + EtOH [PPh4][N3HN3] + Me3SiOEt
12
trans- [Ru(en)2(N2)(N3)] [Sn(N3)6]2-
Metal and non-metal azide compounds
N2 isolated 1790N3
- synthesized 1890N5
+ synthesized 1999
[N2F]+[SbF6] + HN3 [N5]+[SbF6]- + HF(i) Liquid HF 195 K(ii) Warm to 298 K
[N5]+[SbF6]-
[NO]+[SbF6]- + 25N2
[NO2]+[SbF6]- + 25N2
[Br2]+[SbF6]- + 25N2
NO
NO2
Br2
13
Nitrides
Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN
bullHydrolysis of saline hydrides liberates NH3
bullNa3N is hygroscopic
Na3N + 3H2O 3NaOH + NH3
bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities
Pernitrides [N2]2- are known for Sr Ba
bullConditions of 5600 bar of N2 at 920 K for BaN2
Si3N4 are used in glow plugs
titanium nitride coated saw blades
Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures
bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages
Phosphides
bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities
bull Group 1 metals form M3P and Group 2 metals form M3P2
bull Are hydrolyzed by water and can be considered ionic
httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract
14
Gallium Arsenide
bull Important group III-V semiconductor that crystallizes with zinc-blende structure
bull Band gap of 142 eV thus can be used to make devices that emit light in the infrared region
bull Exhibits high electron mobility 8500 cm2V-1s-1 vs silicon 1500 cm2V-1s-1
bull Disadvantages of GaAs vs Sibull Expensivebull Brittlebull Lower Thermal Conductivity
bull Highest-efficiency single-junction solar cell at 288
bull httpdxdoiorg1011092FPVSC20126317891
Unit cell of NiAs
Ni
As
NiAs (nickel arsenide)
15
[Sb8]2 or [Bi8]2 Pd-centered pentagonal antiprismatic structure of
[PdBi10]4
16
Selected reactions of PCl5
SbF54
[Sb2F11] [As6I8]2
17
[BiCl3(15-crown-5)] [BiCl3L]
Oxides of Nitrogen
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
10
[P3H3]2-
Potential diagram for nitrogen at pH = 0
Latimer (or reduction potential diagrams) show the standard reduction potentials connecting various oxidation states of an element
Is hydroxlamine [NH3OH]+ stable with respect to disproportionation to N2 and [N2H5]+ amp [NH4]+
11
HN3
[N3]
[N3HN3]
[PPh4][N3] + Me3SiN3 + EtOH [PPh4][N3HN3] + Me3SiOEt
12
trans- [Ru(en)2(N2)(N3)] [Sn(N3)6]2-
Metal and non-metal azide compounds
N2 isolated 1790N3
- synthesized 1890N5
+ synthesized 1999
[N2F]+[SbF6] + HN3 [N5]+[SbF6]- + HF(i) Liquid HF 195 K(ii) Warm to 298 K
[N5]+[SbF6]-
[NO]+[SbF6]- + 25N2
[NO2]+[SbF6]- + 25N2
[Br2]+[SbF6]- + 25N2
NO
NO2
Br2
13
Nitrides
Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN
bullHydrolysis of saline hydrides liberates NH3
bullNa3N is hygroscopic
Na3N + 3H2O 3NaOH + NH3
bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities
Pernitrides [N2]2- are known for Sr Ba
bullConditions of 5600 bar of N2 at 920 K for BaN2
Si3N4 are used in glow plugs
titanium nitride coated saw blades
Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures
bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages
Phosphides
bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities
bull Group 1 metals form M3P and Group 2 metals form M3P2
bull Are hydrolyzed by water and can be considered ionic
httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract
14
Gallium Arsenide
bull Important group III-V semiconductor that crystallizes with zinc-blende structure
bull Band gap of 142 eV thus can be used to make devices that emit light in the infrared region
bull Exhibits high electron mobility 8500 cm2V-1s-1 vs silicon 1500 cm2V-1s-1
bull Disadvantages of GaAs vs Sibull Expensivebull Brittlebull Lower Thermal Conductivity
bull Highest-efficiency single-junction solar cell at 288
bull httpdxdoiorg1011092FPVSC20126317891
Unit cell of NiAs
Ni
As
NiAs (nickel arsenide)
15
[Sb8]2 or [Bi8]2 Pd-centered pentagonal antiprismatic structure of
[PdBi10]4
16
Selected reactions of PCl5
SbF54
[Sb2F11] [As6I8]2
17
[BiCl3(15-crown-5)] [BiCl3L]
Oxides of Nitrogen
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
11
HN3
[N3]
[N3HN3]
[PPh4][N3] + Me3SiN3 + EtOH [PPh4][N3HN3] + Me3SiOEt
12
trans- [Ru(en)2(N2)(N3)] [Sn(N3)6]2-
Metal and non-metal azide compounds
N2 isolated 1790N3
- synthesized 1890N5
+ synthesized 1999
[N2F]+[SbF6] + HN3 [N5]+[SbF6]- + HF(i) Liquid HF 195 K(ii) Warm to 298 K
[N5]+[SbF6]-
[NO]+[SbF6]- + 25N2
[NO2]+[SbF6]- + 25N2
[Br2]+[SbF6]- + 25N2
NO
NO2
Br2
13
Nitrides
Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN
bullHydrolysis of saline hydrides liberates NH3
bullNa3N is hygroscopic
Na3N + 3H2O 3NaOH + NH3
bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities
Pernitrides [N2]2- are known for Sr Ba
bullConditions of 5600 bar of N2 at 920 K for BaN2
Si3N4 are used in glow plugs
titanium nitride coated saw blades
Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures
bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages
Phosphides
bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities
bull Group 1 metals form M3P and Group 2 metals form M3P2
bull Are hydrolyzed by water and can be considered ionic
httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract
14
Gallium Arsenide
bull Important group III-V semiconductor that crystallizes with zinc-blende structure
bull Band gap of 142 eV thus can be used to make devices that emit light in the infrared region
bull Exhibits high electron mobility 8500 cm2V-1s-1 vs silicon 1500 cm2V-1s-1
bull Disadvantages of GaAs vs Sibull Expensivebull Brittlebull Lower Thermal Conductivity
bull Highest-efficiency single-junction solar cell at 288
bull httpdxdoiorg1011092FPVSC20126317891
Unit cell of NiAs
Ni
As
NiAs (nickel arsenide)
15
[Sb8]2 or [Bi8]2 Pd-centered pentagonal antiprismatic structure of
[PdBi10]4
16
Selected reactions of PCl5
SbF54
[Sb2F11] [As6I8]2
17
[BiCl3(15-crown-5)] [BiCl3L]
Oxides of Nitrogen
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
12
trans- [Ru(en)2(N2)(N3)] [Sn(N3)6]2-
Metal and non-metal azide compounds
N2 isolated 1790N3
- synthesized 1890N5
+ synthesized 1999
[N2F]+[SbF6] + HN3 [N5]+[SbF6]- + HF(i) Liquid HF 195 K(ii) Warm to 298 K
[N5]+[SbF6]-
[NO]+[SbF6]- + 25N2
[NO2]+[SbF6]- + 25N2
[Br2]+[SbF6]- + 25N2
NO
NO2
Br2
13
Nitrides
Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN
bullHydrolysis of saline hydrides liberates NH3
bullNa3N is hygroscopic
Na3N + 3H2O 3NaOH + NH3
bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities
Pernitrides [N2]2- are known for Sr Ba
bullConditions of 5600 bar of N2 at 920 K for BaN2
Si3N4 are used in glow plugs
titanium nitride coated saw blades
Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures
bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages
Phosphides
bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities
bull Group 1 metals form M3P and Group 2 metals form M3P2
bull Are hydrolyzed by water and can be considered ionic
httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract
14
Gallium Arsenide
bull Important group III-V semiconductor that crystallizes with zinc-blende structure
bull Band gap of 142 eV thus can be used to make devices that emit light in the infrared region
bull Exhibits high electron mobility 8500 cm2V-1s-1 vs silicon 1500 cm2V-1s-1
bull Disadvantages of GaAs vs Sibull Expensivebull Brittlebull Lower Thermal Conductivity
bull Highest-efficiency single-junction solar cell at 288
bull httpdxdoiorg1011092FPVSC20126317891
Unit cell of NiAs
Ni
As
NiAs (nickel arsenide)
15
[Sb8]2 or [Bi8]2 Pd-centered pentagonal antiprismatic structure of
[PdBi10]4
16
Selected reactions of PCl5
SbF54
[Sb2F11] [As6I8]2
17
[BiCl3(15-crown-5)] [BiCl3L]
Oxides of Nitrogen
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
13
Nitrides
Li3N Na3N Be3N2 Mg3N2 Ca3N2 Ba3N2 and AlN
bullHydrolysis of saline hydrides liberates NH3
bullNa3N is hygroscopic
Na3N + 3H2O 3NaOH + NH3
bullNitrides of d-block metals are hard inert solids with high melting points and electrical conductivities
Pernitrides [N2]2- are known for Sr Ba
bullConditions of 5600 bar of N2 at 920 K for BaN2
Si3N4 are used in glow plugs
titanium nitride coated saw blades
Most elements (except Hg Pb As Te) combine with P to form phosphidesbull Variety of solid state structures
bull The alkali metals can also form phosphides which contain groups of P atoms (eg [P7]3- and [P11]3-) as chains or cages
Phosphides
bull Phosphides with d-block metals tend to be inert metallic looking with high melting point and electrical conductivities
bull Group 1 metals form M3P and Group 2 metals form M3P2
bull Are hydrolyzed by water and can be considered ionic
httppubsrscorgencontentarticlelanding2010csb916787kdivAbstract
14
Gallium Arsenide
bull Important group III-V semiconductor that crystallizes with zinc-blende structure
bull Band gap of 142 eV thus can be used to make devices that emit light in the infrared region
bull Exhibits high electron mobility 8500 cm2V-1s-1 vs silicon 1500 cm2V-1s-1
bull Disadvantages of GaAs vs Sibull Expensivebull Brittlebull Lower Thermal Conductivity
bull Highest-efficiency single-junction solar cell at 288
bull httpdxdoiorg1011092FPVSC20126317891
Unit cell of NiAs
Ni
As
NiAs (nickel arsenide)
15
[Sb8]2 or [Bi8]2 Pd-centered pentagonal antiprismatic structure of
[PdBi10]4
16
Selected reactions of PCl5
SbF54
[Sb2F11] [As6I8]2
17
[BiCl3(15-crown-5)] [BiCl3L]
Oxides of Nitrogen
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
14
Gallium Arsenide
bull Important group III-V semiconductor that crystallizes with zinc-blende structure
bull Band gap of 142 eV thus can be used to make devices that emit light in the infrared region
bull Exhibits high electron mobility 8500 cm2V-1s-1 vs silicon 1500 cm2V-1s-1
bull Disadvantages of GaAs vs Sibull Expensivebull Brittlebull Lower Thermal Conductivity
bull Highest-efficiency single-junction solar cell at 288
bull httpdxdoiorg1011092FPVSC20126317891
Unit cell of NiAs
Ni
As
NiAs (nickel arsenide)
15
[Sb8]2 or [Bi8]2 Pd-centered pentagonal antiprismatic structure of
[PdBi10]4
16
Selected reactions of PCl5
SbF54
[Sb2F11] [As6I8]2
17
[BiCl3(15-crown-5)] [BiCl3L]
Oxides of Nitrogen
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
15
[Sb8]2 or [Bi8]2 Pd-centered pentagonal antiprismatic structure of
[PdBi10]4
16
Selected reactions of PCl5
SbF54
[Sb2F11] [As6I8]2
17
[BiCl3(15-crown-5)] [BiCl3L]
Oxides of Nitrogen
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
16
Selected reactions of PCl5
SbF54
[Sb2F11] [As6I8]2
17
[BiCl3(15-crown-5)] [BiCl3L]
Oxides of Nitrogen
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
17
[BiCl3(15-crown-5)] [BiCl3L]
Oxides of Nitrogen
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
18
[N2O2]2-
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
19
HNO3
NO3-
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
20
oxoacids of phosphorus
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
21
[W3(OH2)9NiSe4PH(OH)2]4
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
22
enantiomers (non-superimposable mirror images)
unit cell of FeSb2O6 unit cell of NaSbO3
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
23
[Cl3PNPCl2NPCl3]
[Cl3PN(PCl2N)2PCl3]Proposed reaction scheme for the formation of the cyclic phosphazene (NPCl2)3
phosphazenes (NPX2)3 P4N4 ring conformations
P+
P+
P+N-
N-
N-
24
(R)-[Sb(O2CCF3)3] Bi2(O2CCF3)4 [Bi2(C6H4O2)4]2
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