中级无机化学唐宗薰版课后习题第九章答案

㄀9ゴд乬

1䅵ㅫϟ ⠽ⱘӋ⬉ ˈ ѯヺ FAN 㾘 DŽ

㾷˖(1) V(CO)6 V ˖5ˈ6CO ˖12˗ 17DŽϡヺ

(2) W(CO)6 W ˖6ˈ6CO ˖12˗ 18DŽヺ

(3) Ru(CO)4H Ru ˇ˖7ˈ4CO ˖8ˈH ˉ˖2˗ 17DŽϡヺ

(4) Ir(CO)(PPh 3)2Cl Ir ˇ˖8ˈCO ˖2ˈ2PPh 3˖4ˈCl ˉ˖2˗ 16DŽヺ

(5) Ni(Ș5-C 5H 5)(NO) Ni ˇ˖9ˈC 5H 5ˉ˖6ˈNO ˖3˗ 18DŽヺ

(6) PtCl 3(Ș2-C 2H 4)ˉ Pt 2ˇ˖8ˈ3Cl ˉ˖6ˈC 2H 4˖2˗ 16DŽヺ

2ϟ ㇛ ⠽Ё ѯ M ˙M 䬂?ЎҔМ?

㾷˖(1) Fe 3(CO)123h 8 (Fe)ˇ12h 2 (CO)˙48 (3h 18ˉ48)/2˙3ˈ

ϝ 䬂䖲 ϝϾFe ˈϝϾFe ϝ㾦 ˈˈ 䆹 M ˙M 䬂˗(2) H ˇ2[Os 3(CO)10]2ˉ3h 8 (Os)ˇ10h 2 (CO)ˇ2(䋳⬉㥋)˙46 (3h 18ˉ46)/2˙4ˈ

䬂䖲 ϝϾOs ˈϝϾOs ϝ㾦 ˈˈ 䆹 ϔ M ˙M 䬂˗

(3) H ˇ4[Re 4(CO)12]4ˉ4h 7 (Re)ˇ12h 2 (CO)

ˇ4(䋳⬉㥋)˙56 (4h 18ˉ56)/2˙8ˈ

䬂䖲 ϾRe ˈ ϾRe 䴶ԧ ˈˈ 䆹 ϸ M ˙M 䬂˗

(4) [Re 4(CO)16]2ˉ4h 7 (Re)ˇ16h 2 (CO)ˇ2(䋳⬉㥋)˙62 (4h 18ˉ62)/2˙5

Ѩ 䬂䖲 ϾRe ˈ ϾRe 㵊 ˈˈ 䆹 M ˙M 䬂DŽ

3 [HFe 4(CO)13]ˉ H 3Os 4(CO)12I ḋⱘ㒧 ˛⬏ 䇈 ПDŽ

㾷˖ 㵊 ⱘ㒧 ˖

4䞥 㖄 ⠽ЁˈCO 䞥 ⱘ䜡ԡ ⾡˛ ҔМ˛В՟䇈 DŽ

㾷˖ 䞥 㖄 ⠽ЁˈCO 䗮 ϟ ⼎ⱘѨ⾡䜡ԡ ˖ ッ ǃ䖍ḹ ǃ ḹ ǃ䴶ḹ ջ 䜡ԡ˖

5ㅔ䗄[Re 2Cl 8]2ˉ

ⱘ 䬂䖛⿟ˈ䇈 ⱘ ˈЎҔМ 䞡 ⱘ˛

㾷˖ 㾕 к9.7.1㡖lj䞥 ˉ䞥 䬂NJЁ [Re 2Cl 8]2ˉЁⱘ䞥 䬂ⱘ 䗄DŽ

6 ㄨϟ 䯂乬:

(1)ЎҔМ㖄 ⠽Ё䖛⏵ ㋴ ҹ 䳊Ӌ( Fe(CO)5) 㗙 䋳Ӌ( [Co(CO)4]ˉ)˛(a)[HFe 4(CO)13]ˉ(H ⬏ ) (b)H 3Os 4(CO)12I ⱘ㒧

C O

M M

(a)(b)(c)(d)(e) CO 䞥 ⱘ ⾡䜡ԡ (a) ッ 䜡ԡ (b) 䖍ḹ 䜡ԡ

(c) ḹ 䜡ԡ(d)䴶ḹ 䜡ԡ(e)ջ 䜡ԡ

ㄨ˖㖄 䜡ԧЎʌˉ䝌䜡ԧˈ 㞾Ё 䞥 ⱘd(p)⬉ 作ʌˉ䬂ˈıˉʌ 䬂ⱘ㒧 Փ ⠽㛑〇 DŽ佪 ˈ 䞥 Ў0Ӌ 䋳Ӌ ˈ ԭⱘd⬉ ҹ 作 ˗ ⃵ˈ 䞥 Ў0Ӌ 䋳Ӌ ˈӋ䔼䘧䕗Ў ˈ Ѣ䔼䘧䞡 DŽⳌ ˈ 䞥 Ў催Ӌ ˈ ≵ ԭd⬉ 作 ˈ Ӌ䔼䘧 㓽ˈϡ Ѣ䞡 DŽ

(2)ЎҔМ䞥 MnǃTcǃReˈCoǃRhǃIr Ḍ㖄 ⠽˛

ㄨ˖ķ Ḍ㖄 ⠽Ё 䞥 䬂ˈ䖭ѯ ㋴䛑 ⬉ ˈ Ḍ㖄 ⠽ѺЎ ⬉ ˈ ⳌѦ㘮 䞥 䬂DŽ

ĸ 䞥 Ӌ䔼䘧Ёd⬉ ˈ⬉ 䯈ⱘⳌѦ ⹡䞥 䬂ⱘ⫳ ˈ 䞥 Ӌ䔼䘧Ёd ⬉ ˈ䞥 ԭd⬉ 作㒭 Ѣʌˉ䝌䜡ԧⱘCO⫳ 作ʌ䬂ˈ㗠䖭ѯ ㋴ d⬉ Ў5Ͼ 7Ͼˈϡ ˈгϡ ˈℷ 䗖 作ʌ䬂ⱘ⫳ DŽ

(3)ЎҔМCOǃRNC PF3㛑 ㉏Ԑⱘ 䞥 䜡 ⠽˛

ㄨ˖ Ӏ Ѣʌˉ䝌䜡ԧ ҹⳌ ⱘıˇʌⱘ 䬂 䬂ˈ ℸ㛑 ㉏Ԑⱘ 䞥 䜡 ⠽DŽ

7 CO ϔ⾡ ϡ⌏⋐ⱘ ⠽ˈЎҔМ 㛑 䖛⏵䞥 ⱘ䜡ԡ䬂˛CO䜡ԡ 䜡ԡ C䖬 O˛ЎҔМ˛

ㄨ˖ CO ϔϾʌˉ䝌䜡ԧˈıˇʌⱘ 䬂 Փ 䜡ԡ䬂 DŽCO ҹC԰Ў䜡ԡ ⱘˈ䖭 ЎOⱘ⬉䋳 ˈ ⬉ ⱘ㛑䞣ԢП DŽ

8㾷䞞ϟ џ :

(1) V(CO)6 䖬 Ў[V(CO)6]ˉˈԚV2(CO)12䖬ϡ V(CO)6〇 ˗

ㄨ˖V(CO)6 5ˇ12˙17eˈ ⬉ ⒵䎇EAN㾘 ⱘV(CO)6ˉDŽV2(CO)12㱑✊⒵䎇EAN㾘 ˈԚϸϾV䯈 ϔ 䞥 䬂ˈVⱘ䜡ԡ Ў7ˈϢ䜡ԡ Ў6ⱘV(CO)6Ⳍ↨ˈぎ䯈䖛 ˈぎ䯈ԡ䰏԰⫼Փ 〇 DŽ

(2)䗮 Niϡ ⇻ ЎNi3ˇˈԚNi(C5H5)2ЁⱘNi2ˇ ⇻ ˈ 䔼䘧㉏ԐѢѠ㣖䪕DŽ

ㄨ˖Ni(C5H5)2 20Ͼ⬉ ˈ 䬂 䔼䘧Ё ϸϾ ⬉ ˈ 㹿⇻ 㗠 ⬉ ˈ ҹ 䬂Ёⱘ⬉ ˈ 䬂㑻ˈҢ㗠 ⱘ〇 DŽ

(3) WCp2H2 ReCp2H 㒧 DŽ

ㄨ˖WⱘϸϾHˉ䜡ԡ⾏ Reⱘ1ϾHˉ䜡ԡ⾏ Փ ϸϾCpϡ 㸠DŽ

9ⷨお ∂䜡 ⠽ ҔМ Н˛

㾷˖ⷨお ∂䜡 ⠽ Ѣ ⦄⏽ ӊϟ ῵ ⫳⠽ ∂ ⴔ䴲 䞡 ⱘ НDŽ

10 ԩ Ѡ㣖䪕 㫵 Ⲥ˛↨䕗Ѡ㗙 䬂 ⱘ ⚍DŽ

㾷˖Ѡ㣖䪕ⱘ ⊩ ˈ

(1)⺅䞥 Ⲥ⊩

⫼⦃ Ѡ⛃䩴 ∈䞥 ⠽ 㖄 ⠽ THFЁ ˖

THF

FeX2ˇ 2NaC5H5(Ș5-C5H5)2Feˇ 2NaX

(2)㛎Ⲥ⊩

ϮϞ⫼䪕㉝ Э㛎Ⲥ❨㵡ˈѻ⫳ ∈FeCl2ˈ✊ ⺅ 䆩 ⺅(Et2NH) ϟϢ⦃ Ѡ⛃԰⫼ 䞥 㣖DŽ

Feˇ 2 Et2NHǜHCl FeCl2ˇH2ˇ 2 Et2NH

FeCl2ˇ 2 C5H6ˇ 2Et2(Ș5-C5H5)2Feˇ 2 Et2NH2Cl

Ё 㛎Et2NH㛑⿏ ⦃ Ѡ⛃Ϟⱘ⇶ 䰸 Ё⫳ ⱘHClˈՓ 䕗Ԣ⏽ ϟ䖯㸠DŽ ⊩ Ў䪕㉝ˈӋḐ ˈϨ㛎Ⲥ㛑 ⦃Փ⫼DŽ

(3)Ḑ⇣䆩 ⊩

⫼Ḑ⇣䆩 C5H5MgBrϢFeCl3԰⫼ Ѡ㣖䪕DŽ ЁˈFe3ˇ㹿Ḑ⇣䆩 䖬 ЎFe2ˇˈ ϢC5H5MgBr ⫳ њ(Ș5-C5H5)2Fe˖