Trigonal-planar (D₃ₕ) kompleks birikmalar

jdakimyo.uz · Koordinatsion soni 3 · sp² gibridlanish · d¹⁰ tizim

▲ K.Ch = 3sp² gibridD₃ₕ · |G|=12d¹⁰ · μ_eff = 018-elektron qoidasi

Uch koordinatsiyali tekis uchburchak (∠L–M–L = 120°)

Koordinatsion soni 3 ga teng bo'lgan komplekslarda markaziy metallning uchta bog'lash o'rni bir tekislikda joylashib, D₃ₕ nuqta guruhiga xos ideal 120° burchak hosil qiladi. Bu geometriya markaziy atomning sp² gibridlanishi bilan izohlanadi va p_z orbital tekislikka perpendikulyar holda π-simmetriyali bog'lanishlar uchun ochiq qoladi. Trigonal-planar shakl asosan d¹⁰ konfiguratsiyali og'ir metallar ionlarida (Cu⁺, Ag⁺, Au⁺, Hg²⁺) va past valentli platina guruhi (Pt⁰, Pd⁰) komplekslarida uchraydi. 18-elektron qoidasiga muvofiq d¹⁰ + 3×2 = 16 elektron — bu barqaror konfiguratsiyaning to'ldiruvchi hisoblanadi.

CFSE: 0 (d¹⁰)

Δₜₚ: ≈ 0.44·Δₒ

Jahn-Teller: Yo'q

Bogʻ: σ + π-back-donation

3D sahna yuklanmoqda…

⚙️ Boshqaruv paneli

⋮⋮ sudrang

Kompleks

Tuz: K₂[Cu(CN)₃]·H₂O

Rang: Rangsiz kristall

d-config: d¹⁰

M-L: 1.935 Å

Avto aylanishYorliqlarTashqi sfera (K⁺)Tooltip

Ko'rinish rejimi

📚1. Nazariy asoslar — chuqur tahlil

VSEPR (Gillespie–Nyholm) — matematik model

AX₃E₀ turdagi molekulalar uchun uchta bog'lovchi elektron juftining o'zaro Coulomb itarilishi minimallashishi shartida ular D₃ₕ simmetriyali tekislikda 120° burchak ostida joylashadi.

V(θ) = k·Σᵢ<ⱼ 1/rᵢⱼ → min pri Σᵢcos(θᵢⱼ) = −3/2 → θ = 120°

Ligandlar π-tarkibga ega bo'lsa (CN⁻, CO), simmetriya sof saqlanadi. Sof σ-donorlarda ham burchak ideal 120° dan < 0.5° chetlanadi.

Gibridlanish — sp² to'lqin funksiyalari

ψ₁ = (1/√3)s + (√2/√3)pₓ

ψ₂ = (1/√3)s − (1/√6)pₓ + (1/√2)p_y

ψ₃ = (1/√3)s − (1/√6)pₓ − (1/√2)p_y

Ortonormal: ⟨ψᵢ|ψⱼ⟩ = δᵢⱼ. s-tarkib 33.3%, p-tarkib 66.7%. Uchinchi p_z orbital tekislikka perpendikulyar — π-back-donation uchun ochiq.

CFT: D₃ₕ da d-orbital bo'linishi

Sferik simmetriyadagi 5 ta d-orbital D₃ₕ maydonda 3 ta darajaga bo'linadi:

e' (d_xy, d_x²−y²) E = +0.546 Δₜₚ (yuqori)

a₁' (d_z²) E = −0.321 Δₜₚ (o'rta)

e″ (d_xz, d_yz) E = −0.386 Δₜₚ (past)

Δₜₚ ≈ 4/9·Δₒ ≈ 0.44 Δₒ — oktaedrikga nisbatan zaifroq.

CFSE(d¹⁰) = 4(−0.386) + 2(−0.321) + 4(+0.546) ≈ 0 Δₜₚ

MO nazariyasi — SALC tahlili

D₃ₕ da 3 ta σ-ligand simmetriya-moslashtirilgan chiziqli kombinatsiyalari:

Γσ = a₁' + e'

φ(a₁') = (1/√3)(σ₁+σ₂+σ₃)

φ(e'ₐ) = (1/√6)(2σ₁−σ₂−σ₃)

φ(e'ᵦ) = (1/√2)(σ₂−σ₃)

Metall AO simmetriyalari:

s → a₁', (pₓ,p_y) → e', p_z → a₂″
d_z² → a₁', (d_xy,d_x²−y²) → e', (d_xz,d_yz) → e″

18-elektron qoidasi — istisno

Trigonal-planar d¹⁰ komplekslar 16-elektron tizimi (koordinatsion to'yinmagan):

d¹⁰ + 3×2σ = 16 e⁻ (18e⁻ dan 2 kam)

Bu katalizga asos: 16e⁻ ↔ 18e⁻ tebranishi oksidativ qo'shilish / qaytariluvchi ajralish jarayonlarini ta'minlaydi (Suzuki, Heck, Negishi, Wacker).

Misol: [Pt(PPh₃)₃] (16e⁻) + H₂ → [Pt(H)₂(PPh₃)₃] (18e⁻)

Relyativistik effektlar — Pyykkö tahlili

Cu, Ag, Au, Hg, Pt uchun relyativistik ta'sirlar:

6s-orbital qisqarishi (Au: 15%) — ns AO past koordinatsion sonda faolroq
5d-orbital kengayishi — π-back-donation kuchayadi
Spin-orbital juftlashuv: ξ(Pt) ≈ 5000 sm⁻¹

Xulosa: og'ir metallar past koordinatsion sonda (2, 3, 4) barqarorroq — shu sabab Au(I), Cu(I) trigonal-planar shakli qulay.

📐2. Geometrik, energetik va spektroskopik parametrlar

Parametr	Qiymat	Izoh
Koordinatsion son	3	Uchta monodentat ligand
Bog' burchagi	∠L–M–L = 120.0°	Ideal, D₃ₕ
Simmetriya guruhi	D₃ₕ	\|G\| = 12
Gibrid	sp²	33% s + 67% p
Ligand maydon energiyasi	Δₜₚ ≈ 0.44 Δₒ	Zaifroq
CFSE (d¹⁰)	≈ 0	Stabilizatsiya yo'q
18e⁻ qoidasi	16 e⁻ (istisno)	Koordinatsion to'yinmagan
Jahn-Teller	Yo'q (d¹⁰)	Orbital degeneratsiya yo'q
Xarakteristik metallar	Cu⁺, Ag⁺, Au⁺, Hg²⁺, Pt⁰, Pd⁰	d¹⁰ ionlar
Normal tebranishlar	3N−6 = 6	N=4
Vibratsion tasnif	Γ = A₁' + A₂″ + 2E'	Raman/IR faollik
Magnit	Diamagnit	μ_eff = 0 μ_B
Dipol moment (μ)	0 D	Uchta bir xil ligand

⚛️3. sp² gibridlanish sxemasi va energetik diagramma

📊4. Molekulyar orbital diagramma (D₃ₕ)

🌈5. IR / Raman spektri — [Cu(CN)₃]²⁻

IR chastotalar (sm⁻¹)

2094ν(C≡N) sym A₁'kuchsiz (Raman-faol)

2076ν(C≡N) asym E'juda kuchli

390ν(Cu–C) sym A₁'Raman-faol

365ν(Cu–C) asym E'IR-faol

120δ(C–Cu–C) E'uzoq IR

Normal tebranishlar tahlili

Γ_vib = A₁' + A₂″ + 2E' (E' — 2-karrali)

ν₁ (A₁') — simm. cho'zilish, faqat Raman-faol
ν₂ (A₂″) — tekislikdan chiqib egilish, faqat IR
ν₃ (E') — asimm. cho'zilish, IR + Raman
ν₄ (E') — tekislikda egilish, IR + Raman

D₃ₕ da inversiya markazi yo'q — o'zaro istisno qoidasi qat'iy emas.

💜6. UV-Vis spektri va elektron o'tishlar — [Cu(CN)₃]²⁻

Yutilish spektri (λ, ε)

λ = 240 nmε = 12,500

MLCT (Cu 3d → CN π*)

λ = 210 nmε = 8,300

π → π* (CN⁻)

Elektron o'tishlar

d¹⁰ tizimda d–d o'tishlar mumkin emas. Yutilish tarmoqlari:

MLCT (dₙ → π* ligand), ε ≈ 10³–10⁴
LMCT (π ligand → sₙ metall), π-donor ligandlarda
π → π* ligand ichida (CN⁻, PPh₃)
d → s/p Rydberg-tipli o'tishlar

🔥7. Termodinamik va kinetik xarakteristikalar

Stabillik konstantalari — [Cu(CN)₃]²⁻

log K₁ = 5.63 (1-bosqich)

log K₂ = 10.53

log K₃ = 13.61

β₃ = 4.07e+13

ΔH° = -85.2 kJ/mol

ΔS° = 45.6 J·mol⁻¹·K⁻¹

ΔG° = ΔH°−TΔS° = -98.8 kJ/mol (298 K)

Ligand almashinuv kinetikasi

16e⁻ komplekslar labil:

k ≈ 10⁶–10⁹ s⁻¹ (Cu⁺, Ag⁺)
Mexanizm: assotsiativ (A/Iₐ) — 4-koordinatsiyali oraliqli
Pt(0), Pd(0): oksidativ qo'shilish (16→18 e⁻)

Eyring: k = (kᵦT/h)·exp(−ΔG‡/RT), ΔG‡ ≈ 25–45 kJ/mol

🔮8. Walsh diagrammasi va Jahn-Teller tahlili

Walsh diagrammasi: D₃ₕ ↔ C₃ᵥ

Molekula piramidalanganda MO energiyalari o'zgarishi:

6 e⁻ (BF₃, BCl₃) → tekis D₃ₕ

8 e⁻ (NH₃, PF₃) → piramidal C₃ᵥ

16 e⁻ (d¹⁰ ML₃) → tekis D₃ₕ

18 e⁻ (d¹⁰ + p_z²) → piramidal

Jahn-Teller teoremasi (1937)

Orbital degenerativ elektron holatda molekula simmetriyani pasaytiradi.

d¹⁰ da:

Barcha d-orbitallar to'la
Orbital degeneratsiya yo'q
J-T effekti kuzatilmaydi

Istisno holatlar:

d⁹ ML₃ (E' holat) → Y-buzilish yoki T-shaped
d⁷ past-spin ML₃ → analogik

Panelda "Jahn-Teller" ni yoqib, gipotetik buzilishni ko'ring.

📊9. Spektrokimyoviy qator va ligand maydonining kuchi

Ligandlarning kristall maydonini yaratish qobiliyati bo'yicha qatorlangan (Δₒ normalize):

I⁻

0.42 Δₒ

π-donor

Br⁻

0.48 Δₒ

π-donor

Cl⁻

0.53 Δₒ

π-donor

F⁻

0.63 Δₒ

π-donor

H₂O

0.70 Δₒ

kuchsiz π-donor

NH₃

0.90 Δₒ

faqat σ-donor

0.93 Δₒ

σ-donor

PPh₃

1.15 Δₒ

σ-donor + π-akseptor

CN⁻

1.50 Δₒ

π-akseptor (kuchli)

1.55 Δₒ

π-akseptor (kuchli)

Kuchayish tartibi: I⁻ < Br⁻ < Cl⁻ < F⁻ < H₂O < NH₃ < en < PPh₃ < CN⁻ < CO

🧪10. Trigonal-planar komplekslarning to'liq to'plami

[Cu(CN)₃]²⁻

D₃ₕ

Kaliy tritsianokuprat(I) monohidrat

Markaz: Cu+1

Bog': 1.935 Å

Gibrid: sp²

d-config: d¹⁰

β₃: 4.1e+13

Rang: Rangsiz

ν(M–L) ≈ 390 sm⁻¹

[HgI₃]⁻

D₃ₕ (buzilgan C₂ᵥ)

Kaliy triyodomerkurat(II)

Markaz: Hg+2

Bog': 2.724 Å

Gibrid: sp² (+ 5d aralashuvi)

d-config: d¹⁰

β₃: 4.0e+27

Rang: To'q

ν(M–L) ≈ 138 sm⁻¹

[Pt(PPh₃)₃]

D₃ (approx. D₃ₕ)

[Pt(PPh₃)₃] — Malatesta kompleksi

Markaz: Pt0

Bog': 2.263 Å

Gibrid: sp² (dₓᵧ + dₓ²₋ᵧ² aralashuvli)

d-config: d¹⁰

β₃: 3.2e+24

Rang: Sariq-jigarrang

ν(M–L) ≈ 517 sm⁻¹

[Ag(CN)₃]²⁻

D₃ₕ

Kaliy tritsianoargentat(I)

Markaz: Ag+1

Bog': 2.135 Å

Gibrid: sp² (5d aralashuvli)

d-config: d¹⁰

β₃: 5.0e+21

Rang: Rangsiz

ν(M–L) ≈ 360 sm⁻¹

⚗️11. Sintez usullari va olinish reaksiyalari

CuCl + 2 KCN → K[Cu(CN)₂] (chiziqli, K.Ch=2)

Birinchi bosqich

K[Cu(CN)₂] + KCN(ort.) → K₂[Cu(CN)₃]

Ortiqcha CN⁻ da trigonal-planar hosil bo'ladi

HgI₂ + KI → K[HgI₃]

Nessler reagentining komponenti

Pt(cod)₂ + 3 PPh₃ → [Pt(PPh₃)₃] + 2 cod

cod = 1,5-siklooktadien; inert atmosferada

AgNO₃ + 3 KCN → K₂[Ag(CN)₃] + KNO₃

Galvanotexnika elektroliti

4 Au + 8 NaCN + O₂ + 2 H₂O → 4 Na[Au(CN)₂] + 4 NaOH

Sianidli oltinni ekstraksiya (MacArthur–Forrest)

[Pt(PPh₃)₃] + O₂ → [Pt(O₂)(PPh₃)₂] + PPh₃

Oksidativ qo'shilish (O₂ faollashuvi)

[Pt(PPh₃)₃] + PhBr → [Pt(Ph)(Br)(PPh₃)₂] + PPh₃

Suzuki katalizining 1-bosqichi

📜12. Tarixiy rivojlanish va zamonaviy qo'llanilish

Tarixiy bosqichlar

1798 — Tassaert: AgCN, K[Ag(CN)₂] birinchi ta'rifi
1893 — A. Werner koordinatsion nazariyasi (Nobel, 1913)
1916 — G. Lewis: donor-akseptor bog' tushunchasi
1931 — L. Pauling: gibridlanish nazariyasi
1937 — Jahn-Teller teoremasi
1957 — Chatt–Duncanson: π-back-donation modeli
1968 — Ugo, Cariati: [Pt(PPh₃)₃] sintezi
1988 — P. Pyykkö: relyativistik effektlar
2010 — Suzuki, Heck, Negishi: Nobel mukofoti (Pd katalizatorlari)

Zamonaviy qo'llanilish

🧪 Kataliz: [Pt(PPh₃)₃], [Pd(PPh₃)₃] — Suzuki, Heck, Sonogashira, Negishi C–C bog'lanishlarida asosiy katalizator
⚗️ Analitik kimyo: Nessler reagenti (K₂[HgI₄] + KOH) — NH₃/NH₄⁺ ni sifat aniqlash (0.02 mg/l)
💍 Metallurgiya: Na[Au(CN)₂] — oltinni sianid usulida ajratish (jahon ishlab chiqarishining ~90%)
💡 OLED: Cu(I), Au(I) trigonal komplekslar — fosforessent emitter (Φ > 90%)
🧬 Tibbiyot: Auranofin — Au(I) revmatoid artrit dorisi; HIV va rak profilaktikasi ilmiy tadqiqotlari
🔬 Biokataliz: Cu(I) — laksase, tirozinaza modellari
🌿 Yashil kimyo: Ag(I), Au(I) NHC — antibakterial agent
💎 Materialshunoslik: Cu(I) siyanid MOF — gaz saqlash, sensor

⚖️13. Fazoviy shakllar taqqoslash jadvali

Shakl	K.Ch	Burchak	Gibrid	Simmetriya	CFSE	Misol
Chiziqli	2	180°	sp	D∞ₕ	0	[Ag(NH₃)₂]⁺
Trigonal-planar	3	120°	sp²	D₃ₕ	0	[Cu(CN)₃]²⁻
Trigonal-piramidal	3	<120°	sp³	C₃ᵥ	—	NH₃ (lp bilan)
Tetraedrik	4	109.5°	sp³	Tₐ	−0.53Δₒ	[Zn(NH₃)₄]²⁺
Kvadrat-planar	4	90°	dsp²	D₄ₕ	−1.22Δₒ	[PtCl₄]²⁻
Trig.-bipiramidal	5	90/120°	dsp³	D₃ₕ	−0.82Δₒ	[Fe(CO)₅]
Oktaedrik	6	90°/180°	d²sp³	Oₕ	−2.40Δₒ	[Co(NH₃)₆]³⁺

🎯14. O'z-o'zini tekshirish savollari

1. Trigonal-planar geometriyada bog' burchagi qanday?

2. Trigonal-planar komplekslar uchun xarakterli gibridlanish:

3. D₃ₕ nuqta guruhi tartibi (|G|) nechaga teng?

4. d¹⁰ trigonal-planar kompleksda CFSE qiymati:

5. Qaysi ligand π-akseptor sifatida eng kuchli?

6. Trigonal-planar d¹⁰ tizim necha valent elektronga ega?

7. Nessler reagentida qaysi kompleks ishlatiladi?

8. Sianidli oltinni ekstraksiya jarayonida hosil bo'lgan asosiy kompleks:

9. d¹⁰ ML₃ tizimida Jahn-Teller effekti:

10. IR spektroskopiyasida A₁' tebranish qanday?

📚15. Ilmiy adabiyotlar va manbalar

Xalqaro darsliklar

Housecroft, C.E.; Sharpe, A.G. Inorganic Chemistry, 5th ed., Pearson, 2018.
Miessler, G.L.; Fischer, P.J.; Tarr, D.A. Inorganic Chemistry, 5th ed., Pearson, 2014.
Cotton, F.A.; Wilkinson, G.; Murillo, C.A.; Bochmann, M. Advanced Inorganic Chemistry, 6th ed., Wiley, 1999.
Greenwood, N.N.; Earnshaw, A. Chemistry of the Elements, 2nd ed., Butterworth-Heinemann, 1997.
Crabtree, R.H. The Organometallic Chemistry of the Transition Metals, 7th ed., Wiley, 2019.
Hartwig, J.F. Organotransition Metal Chemistry, University Science Books, 2010.
Atkins, P.; Overton, T. et al. Shriver & Atkins Inorganic Chemistry, 6th ed., OUP, 2014.

Muhim ilmiy maqolalar

Bowmaker, G.A. et al. J. Chem. Soc. Dalton Trans. 1997, 4227.
Ugo, R. Coord. Chem. Rev. 1968, 3, 319.
Pyykkö, P. Chem. Rev. 1988, 88, 563.
Persson, I. et al. Inorg. Chem. 2002, 41, 3820.
Bertrand, G. et al. Science 2007, 316, 439.
Yam, V.W.-W. et al. Chem. Rev. 2015, 115, 7589.

O'zbek va rus tilidagi manbalar

Parpiyev N.A., Rahimov H.R., Muftaxov A.G. Anorganik kimyo. — T.: O'zbekiston, 2003.
Ismatov N., Yormatova S. Kompleks birikmalar kimyosi. — T.: TDPU, 2015.
Karimov M.M., Nazarov R. Koordinatsion birikmalar kimyosi. — T.: Fan, 2018.
Ключников Н.Г. Химия комплексных соединений. — М.: Химия, 1997.
Скопенко В.В. и др. Координационная химия. — М.: Академкнига, 2007.

Ma'lumotlar bazalari

CSD — Cambridge Structural Database (1.2M+ struktura)
ICSD — Inorganic Crystal Structure Database
IUPAC 2005 — Red Book (Nomenclature of Inorganic Chemistry)
NIST WebBook — spektroskopik ma'lumotlar