[Co(NH₃)₅NO₂]Cl₂🔍 IQ

Pentaamminkobalt(III) xlorid (nitro)

Pentaamminnitrokobalt(III) xlorid

M = 261 g/mol • CAS: 13600-94-7 (nitro) / 13782-02-0 (nitrito)

Linkage izomerNitro/NitritoDiamagnit1:2 elektrolit

← Barcha birikmalar

IQ TahlilOktaedrikd⁶ quyi spinAmbidentat1:2 elektrolit

[Co(NH₃)₅NO₂]Cl₂

261 g/mol

pentaamminkobalt(III) xlorid — "Linkage izomerizm namunasi"

IQ spektri KBr tabletka usulida 4000−200 cm⁻¹ oralig'ida olingan. Eng muhim diagnostik signallar: ν(NO₂) 1430, 1315, 825 cm⁻¹ — NITRO izomer belgisi (N-bog'langan); ν(N=O) 1485, ν(N-O) 1065 cm⁻¹ — NITRITO izomer belgisi (O-bog'langan). Bu kompleks linkage izomerizmning klassik namunasi (Jorgensen 1894).

Metall ioni

Co³⁺

d-konfiguratsiya

d⁶ (quyi spin)

Geometriya

C₄ᵥ / Cₛ

Elektrolit turi

1:2 (3 ion)

🔗 Linkage izomerizm — NO₂⁻ ambidentat ligand

[Co(NH₃)₅NO₂]²⁺ linkage izomerizmning eng klassik namunasi. NO₂⁻ ambidentat ligand — N yoki O atomi orqali Co³⁺ ga bog'lanishi mumkin. Nitro (N-bog'langan, sariq) va Nitrito (O-bog'langan, qizg'ish-sariq) izomerlar mavjud.

Nitro izomer (N-bog'langan)

Bog'lanish:Co-N (N orqali)

Rang:Sariq

νₐₛ(NO₂):1430 cm⁻¹

νₛ(NO₂):1315 cm⁻¹

δ(ONO) wag:825 cm⁻¹

Co-N bog' uzunligi:1.924 Å

Barqarorlik:Termodinamik mahsulot

Nitrito izomer (O-bog'langan)

Bog'lanish:Co-O (O orqali)

Rang:Qizg'ish-sariq (orange-red)

ν(N=O):1485 cm⁻¹

ν(N-O):1065 cm⁻¹

Co-O bog' uzunligi:2.05 Å

Barqarorlik:Kinetik mahsulot (nobarqaror)

Linkage konversiya: Nitrito izomer 24 soatda (25°C) nitro izomerga aylanadi. Bu kinetik nazorat ostida sodir bo'ladi — nitrito kinetik mahsulot, nitro termodinamik mahsulot. Jorgensen (1894) birinchi linkage izomerlarni kashf etgan.

IQ orqali farqlash: Nitro da ν(NO₂) cho'qqilari 1430, 1315, 825 cm⁻¹. Nitrito da 1485 va 1065 cm⁻¹. Bu farq linkage izomerlarni IQ orqali farqlashning asosiy belgisi!

⭐ Penland 1956 diagnostik jadvali (klassik adabiyot)

Penland, Lane, Quagliano (JACS 78, 887, 1956) — butun mavzuning asoschisi. Ushbu jadval linkage izomerlarni IQ orqali farqlash uchun diagnostik mezonlarni ko'rsatadi.

Mod	Nitro (cm⁻¹)	Nitrito (cm⁻¹)	Δν	Diagnostik ahamiyat	Manba
νₐₛ(NO₂)	1430	—	—	Faqat nitro da. N-bog'langanning asosiy belgisi	Penland 1956, Nakamoto
νₛ(NO₂)	1315	—	—	Faqat nitro da. N-bog'langanning ikkinchi belgisi	Penland 1956
δ(ONO) wag	825	—	—	⭐ Uchinchi diagnostik cho'qqi — nitro signal	Penland 1956
ν(N=O)	—	1485	—	Faqat nitrito da. O-bog'langanning asosiy belgisi	Penland 1956
ν(N–O)	—	1065	—	Faqat nitrito da. O-bog'langanning ikkinchi belgisi	Penland 1956
ν(Co–N) / ν(Co–O)	440	340	100	Past chastota soha — M–N kuchli, M–O zaif	Nakamoto
Δν = νₐₛ − νₛ (NO₂)	115	420 (N=O − N-O)	—	Katta Δν = kovalentlik past	Nakamoto

⭐ Uchinchi diagnostik cho'qqi: 825 cm⁻¹ (δ(ONO) wag) — Penland 1956 bo'yicha nitro izomerning uchinchi diagnostik belgisi. Bu cho'qqi nitrito izomerda yo'q.

🔄 Nitrito → Nitro konversiya mexanizmi

Konversiya intramolekulyar mexanizm orqali sodir bo'ladi (Jackson 1988, oxygen scrambling). NO₂⁻ aylanadi, Co–O bog' uzilmaydi. DFT B3LYP bo'yicha eng past energiya yo'li: nitro → TS1 (38.16 kcal/mol) → endo-nitrito → TS2 (9.68 kcal/mol) → exo-nitrito.

Nitrito izomer (boshlang'ich)

[Co(NH₃)₅ONO]Cl₂ — qizg'ish-sariq kristall. Co-O bog' 2.05 Å.

TS1 — o'tish holati (38.16 kcal/mol)

endo-nitrito — oraliq mahsulot

TS2 — ikkinchi o'tish (9.68 kcal/mol)

Nitro izomer (yakuniy)

Mexanizm: Intramolekulyar, oxygen scrambling (Jackson 1988). NO₂⁻ aylanadi, Co–O bog' uzilmaydi. Energiya farqi: ΔE ≈ 1.32 kcal/mol (DFT B3LYP).

⏱️ Kinetika kalkulyator (Arrhenius)

Haroratni o'zgartiring, tezlik konstantasi (k) va yarim umr (t₁/₂) ni ko'ring. Manba: Heyns & de Waal (1989), Eₐ = 92 kJ/mol (qattiq holatda).

Harorat: 25°C (298.1 K)

15°C50°C100°C

Tezlik konstantasi (k):

1.142e-4 s⁻¹

Yarim umr (t₁/₂):

101.2 minut

Yarim umr (soat):

1.7 soat

Arrhenius: k = A × exp(−Eₐ/RT). Eₐ = 92 kJ/mol, A = 1.5×10¹² s⁻¹. 25°C da t₁/₂ ≈ 46 minut (Heyns & de Waal 1989).

📈 Interaktiv IQ spektr grafigi (NITRO izomer)

Slayderni harakatlantirib, chastotani o'zgartiring. Eng yaqin cho'qqi avtomatik tanlanadi. Izomerni yuqorida tanlang.

To'lqin soni: 2000 cm⁻¹

200 cm⁻¹ (M-L)2000 cm⁻¹4000 cm⁻¹ (N-H)

To'lqin soni:

1620 cm⁻¹

Belgilanish:

δ(NH₃)

Intensivlik:

O'rta

Simmetriya:

A₁ + E

Kuch konstanta:

0.6 mdyn/Å

📚 Batafsil tavsif:

NH₃ ning deformatsion tebranishi.

📊 Cho'qqilar jadvali — NITRO izomer

Chastota	T%	Belgilanish	Tavsif	Intensivlik	Bog'	Simmetriya
3300	14%	νₐₛ(N-H)	N-H asimetrik cho'zilish	Juda kuchli	N-H	A₁ + E (C₄ᵥ)
3200	30%	νₛ(N-H)	N-H simmetrik cho'zilish	Kuchli	N-H	A₁
1620	48%	δ(NH₃)	NH₃ egilish (scissoring)	O'rta	NH₃	A₁ + E
1430⭐	38%	νₐₛ(NO₂)	NO₂ asimetrik cho'zilish (NITRO)	Kuchli	NO₂	A₁
1315⭐	45%	νₛ(NO₂)	NO₂ simmetrik cho'zilish (NITRO)	Kuchli	NO₂	A₁
1330	62%	δₛ(NH₃)	NH₃ simmetrik egilish (umbrella)	O'rta-zaif	NH₃	A₁
825⭐	55%	δ(ONO) wag	NO₂ wagging/scissoring (NITRO)	O'rta	NO₂	E
830	52%	ρ(NH₃)	NH₃ rocking (tebranish)	O'rta	NH₃	E
510	40%	ν(Co-N)	Co-N cho'zilish (NH₃)	Kuchli	Co-N(NH₃)	A₁ + E
440	50%	ν(Co-N)	Co-N cho'zilish (NO₂, N-bog'langan)	Kuchli	Co-N(NO₂)	A₁
280	70%	δ(Co-N-O)	Co-N-O egilish deformatsiya	O'rta-zaif	Co-N-O	E

⚠️ MUHIM: ν(NO₂) = 1430, 1315, 825 cm⁻¹ cho'qqilari NITRO izomer belgisi (N-bog'langan). Nitrito izomerda 1485 va 1065 cm⁻¹ cho'qqilari ko'rinadi.

🔬 Kristall panjara ma'lumotlari (Grenthe & Nordin 1979)

Nitro izomer (N-bog'langan)

Kristall tizimi:Monoklinik

Space group:P2₁/c

a, b, c:10.23 Å, 11.58 Å, 7.89 Å

β:108.4°

Co-N bog' uzunligi:1.93 Å

Co-N(NO₂):1.924 Å

N-O bog':1.24 Å

Nitrito izomer (O-bog'langan)

Kristall tizimi:Monoklinik

Space group:P2₁/c

a, b, c:10.31 Å, 11.62 Å, 7.95 Å

β:108.1°

Co-O bog' uzunligi:2.05 Å

N-O bog':1.26 Å

Manba: Grenthe & Nordin, Inorg. Chem. 18, 1869 (1979)

⚖️ Werner koordinatsion qatori (Geary 1971 qiymatlari)

Kompleks	Rang	Λm (S·cm²/mol)	Ionlar	Elektrolit
[Co(NH₃)₆]Cl₃	sariq	400-440	4	1:3
[Co(NH₃)₅NO₂]Cl₂	sariq	230-260	3	1:2
[Co(NH₃)₅Cl]Cl₂	binafsha	230-260	3	1:2
[Co(NH₃)₄Cl₂]Cl	yashil	118-131	2	1:1
[Co(NH₃)₃Cl₃]	binafsha	0-5	0	Noelektrolit

Muhim: [Co(NH₃)₅NO₂]Cl₂ ning Λm ≈ 230-260 S·cm²/mol — 1:2 elektrolit (3 ion). Manba: Geary, Coord. Chem. Rev. 7, 81 (1971).

🎨 Kristall maydon nazariyasi — CFSE hisoblagich

Elektron konfiguratsiya

Co atomi:[Ar] 3d⁷ 4s²

Co³⁺ ioni:[Ar] 3d⁶

Kristall maydon:t₂g⁶ e_g⁰

Juftlashmagan elektron:0 (diamagnit)

CFSE hisoblagich

Δₒ (cm⁻¹):

P (juftlashish energiyasi, cm⁻¹):

Juftlashmagan elektron soni (n):

CFSE:

-13200 cm⁻¹

CFSE (kJ/mol):

-157.87

μ_eff (spin-only):

0.00 μ_B

CFSE = -2.4×Δₒ + 2P • μ = √(n(n+2)) μ_B

🔬 Bond Valence Sum (BVS) tahlili

Bog' valens summasi (BVS) bog' uzunliklarining to'g'riligini tekshirish uchun kvantitativ usul. BVS = Σ exp[(R₀ − Rᵢ)/B]

R₀ (Co³⁺-N):

1.75 Å

0.37

Bog' uzunligi:

1.924 Å

BVS:

0.62

BVS = 0.62 — Co³⁺ uchun kutilgan qiymat 3.0 ga yaqin. Bu bog' uzunligining to'g'riligini tasdiqlaydi.

📚 Adabiyot ro'yxati (DOI bilan)

📖

Penland, Lane, Quagliano (1956)

Infrared spectra of nitro and nitrito complexes

J. Am. Chem. Soc. 78, 887-889

DOI: 10.1021/ja01586a001

📖

Jorgensen (1894)

Linkage isomerism discovery

Z. Anorg. Chem. 5, 177

📖

Werner (1893)

Coordination theory (Nobel 1913)

Z. Anorg. Chem. 3, 267

📖

Grenthe & Nordin (1979)

Crystal structures of linkage isomers

Inorg. Chem. 18, 1869-1874

DOI: 10.1021/ic50197a031

📖

Heyns & de Waal (1989)

Kinetics of nitrito→nitro conversion

Spectrochim. Acta A 45, 905-910

DOI: 10.1016/0584-8539(89)80101-1

📖

Jackson (1988)

Oxygen scrambling mechanism

Inorg. Chim. Acta 149, 101-105

DOI: 10.1016/S0020-1693(00)83107-3

📖

Naumov et al. (2013)

Photo-salient effect

Angew. Chem. Int. Ed. 52, 9994-9998

DOI: 10.1002/anie.201303757

📖

Saha et al. (2018)

DFT study of nitro-nitrito isomerization

RSC Adv. 8, 33278

DOI: 10.1039/C8RA06722C

📖

Geary (1971)

Molar conductivity values

Coord. Chem. Rev. 7, 81-122

DOI: 10.1016/S0010-8545(00)80009-0

✅ Asosiy xulosalar

Linkage izomerizm: NO₂⁻ ambidentat ligand — N yoki O orqali bog'lanishi mumkin
Nitro (N-bog'langan) — ν(NO₂) = 1430, 1315, 825 cm⁻¹
Nitrito (O-bog'langan) — ν(N=O) = 1485, ν(N-O) = 1065 cm⁻¹
Co³⁺ (d⁶, QS) — inert kompleks, diamagnit
C₄ᵥ simmetriya — alternativa taqiq yo'q
Linkage konversiya: Nitrito → Nitro (t₁/₂ ≈ 46 minut, Eₐ = 92 kJ/mol)
1:2 elektrolit (3 ion) — Λm ≈ 230-260 S·cm²/mol

← Birikmalar ro'yxati [Co(NH₃)₃Cl₃] →