读者园地

问 :为什么燃烧 碘量法测定钢铁中硫其结果不能用理论值计算 ?浙江读者———陈琦读者园地　　答 :燃烧 碘量法测定硫的基本原理可用以下反应方程式表示。试样在高温下通氧燃烧生成ＳＯ2 :4ＦｅＳ +7Ｏ2 2Ｆｅ2 Ｏ3+4ＳＯ2 ↑3ＭｎＳ +5Ｏ2 Ｍｎ3Ｏ4 +3ＳＯ2生成的ＳＯ2 在酸性淀粉溶液 (或淀粉水溶液 )中吸收生成Ｈ2 ＳＯ3:ＳＯ2 +Ｈ2 ＯＨ2 ＳＯ3生成的Ｈ2 ＳＯ3用ＫＩＯ3或Ｉ2 标准溶液滴定 :ＫＩＯ3+5ＫＩ +6ＨＣｌ 3Ｉ2 +6ＫＣｌ+3Ｈ2 ＯＨ2 ＳＯ3+Ｉ2 +Ｈ2 ＯＨ2 ＳＯ4 +2ＨＩ过量的Ｉ2 与淀粉指示剂作用呈蓝色 ,指示终点的到达。由…     

NaF-SnCl_2光度法测定磷的方法中,钼磷黄还原为钼磷蓝的反应式应如何表述?

答 :关于钼磷杂多酸还原为钼磷蓝的反应式一般表示为 :(ＮＨ4 ) 3 Ｈ4 [ＰＭｏ2 Ｏ7) 6]+2ＳｎＣｌ2 +4ＨＣｌ　　　　　　 (ＮＨ4 ) 3 Ｈ4 [Ｐ(Ｍｏ2 Ｏ5)·5 (Ｍｏ2 Ｏ7) ]+2ＳｎＣｌ4 +2Ｈ2 Ｏ但有报道认为在有ＮａＦ存在下 ,反应中不可能有ＳｎＣｌ4 或ＳｎＣｌ2 - 6的形式的化合状态 ,因为ＳｎＦ2 - 6的积累稳定常数的对数值ｌｇβ6等于 2 5 ,远高于ＳｎＣｌ2 - 6的积累稳定常数的对数值 (ｌｇβ6=14)。此外 ,一般认为磷钼蓝分子中只有 2个Ｍｏ(Ⅵ )被还原为Ｍｏ(Ⅴ )。但用光度滴定法研究钼磷蓝的结果表明在 12个Ｍｏ(Ⅵ )中有 4个Ｍ…     

自制简易气体量管系列在中学科学素质教育中的应用(二)——Mg、Zn、Fe、Al等金属原子量的测定

2　有关金属原子量测定 (装置同前 )2 1　简易气体量管的制作 (原图 1)2 2　测定原理 (原图 2～ 3所示 )由反应 :Ｍｅ +ｍＨＣｌＭｅＣｌｍ+ｍ/ 2Ｈ2 ↑(ａ)反应前 :Ｐ空 Ｖ0 =ｎ0 ＲＴ0 　Ｐ水 =Ｈ/Ｌ　Ｐ空 +Ｐ水 =1ｎ0 ＲＴ0 =(1-Ｈ/Ｌ)Ｖ0 (1)(ｂ)反应终了 :Ｗｉｇ的Ｍｅ与过量 5ｍｏｌ/ＬＨＣｌ反应 ,生成Ｈ2物质的量为ｎｉ 水位下降了Ｙｉｃｍ ,可有 (2 )成立 :Ｐ混(Ｖ0 +ＳＹｉ) =(ｎ0 +ｎｉ)ＲＴ0Ｐ′水 =(Ｈ -Ｙｉ) /ＬＰ混 +Ｐ′水 =1(ｎ0 +ｎｉ)ＲＴ0 / (Ｖ0 +ＳＹｉ) -Ｙｉ/Ｌ =1-Ｈ/Ｌ (2 )∵Ｙｉ/Ｌ =0∴ (ｎ0 +ｎｉ)ＲＴ0 …     

自制简易气体量管系列在中学科学素质教育中的应用(三)——Al-Mg合金的测定

3　Ａｌ-Ｍｇ合金的测定3.1　简易气体量管的制作 (第 9期原图 1所示 )3.2　测定原理 (第 9期原图 2 - 3所示 )设 :(Ｚ1,Ｚ2 分别为Ｍｅ1Ｍｅ2 价态 ,物质的量之比为Ｘ∶Ｙ)由反应 (Ｍｅ1Ｍｅ2 ) +ｍＨＣｌ→Ｍｅ1ＣｌＺ1·Ｍｅ1ＣｌＺ2 +(Ｚ1Ｘ +Ｚ2 Ｙ) 1 2Ｈ2 ↑(ａ)反应前 :Ｐ空 Ｖ0 =ｎ0 ＲＴ0 (克氏方程 )　Ｐ水 =Ｈ ＬＰ空 +Ｐ水 =1ｎ0 ＲＴ0 =(1-Ｈ Ｌ)Ｖ0 (1)(ｂ)反应终了 :Ｗｉ(ｇ)合金与过量 5ｍｏｌ Ｌ的ＨＣｌ反应 ,生成Ｈ2的物质的量为ｎｉ 水位下降了Ｙｉ ｃｍ可有 (2 )成立 :　　Ｐ混(Ｖ0 +ＳＹｉ) =(ｎ0 +ｎｉ)ＲＴ0Ｐ’水…     

钴基耐蚀合金的分解

钴基耐蚀合金的溶解方法常见的有稀硝酸 (1+1)、ＨＣｌ+ＨＮＯ3=(5～ 10 ) +1或者于大量浓盐酸中分次滴加少量浓硝酸、Ｈ2 ＳＯ4 (1+9) +ＨＣｌ =5 +1、Ｈ3ＰＯ4 +ＨＣｌＯ4 =1+1并滴加数滴ＨＦ。但对约含碳3%、铬 30 %、Ｗ 18%、Ｓｉ 2 %、Ｍｎ≤ 1%和Ｆｅ≤ 2 %的钴基合金的分解上述方法均不适应。本文用不加水的硫磷混合酸并快速升温 ,浓硝酸破坏碳化物 ,方法可操作性强。操作步骤为 :称取试样 0 .1ｇ置于 15 0～ 2 5 0ｍｌ锥形瓶中 ,加硫酸 10ｍｌ ,磷酸收稿日期 :2 0 0 0 0 4 122 0ｍｌ ,于高温电炉上快速 (3～ 7ｍｉｎ)升温至冒浓Ｓ…     

热电池材料FeS2分析方法改进

原热电池材料ＦｅＳ2 的分析 ,是在浓、热ＨＣｌ溶液中 ,用ＳｎＣｌ2 将Ｆｅ3+ 还原为Ｆｅ2 + 。过量的ＳｎＣｌ2用ＨｇＣｌ2 氧化除去 ,再用Ｋ2 Ｃｒ2 Ｏ7标准溶液滴定。测定铁时 ,每一份试液中需加入饱和ＨｇＣｌ2 溶液 10ｍｌ(2 0℃时ＨｇＣｌ2 的溶解度约 6%～ 7% ) ,约有4 80ｍｇ的汞排入下水道 ,而国家环境部门规定 ,汞排放的允许量为 0 .0 5ｍｇ·Ｌ- 1,要达到此排放允许量 ,至少要加入 9ｔ的水稀释。汞盐积累在底泥和水质中 ,造成环境严重污染 ,有害于人的健康。因此无汞测定铁的含量已成为必然趋势。无汞测定铁已有报道 ,可采用三…     

（四甲基二硅撑）双（3—三甲硅基环戊二烯基）—四羰基二铁…

标题化合物（Ｍｅ２ＳｉＳｉＭｅ２）〔η＾５－（３－Ｍｅ３ＳｉＣ５Ｈ３）Ｆｅ（ＣＯ）２〕２／（μ－ＣＯ）２（Ａ）分子中的Ｆｅ－Ｆｅ键被钠汞齐还原断裂，生成相应的双铁负离子，分别与ＭｅＣＯＣｌ、ＰｈＣＯＣｌ、ＰｈＣＨ２Ｃｌ、ＣｌＣＨ２ＣＯＯＣ２Ｈ５和Ｐｈ３ＳｎＣｌ进行亲核取代反应，生成在铁原子上引入相应取代基的产物（Ｍｅ２ＳｉＳｉＭｅ２）〔η＾５－（３－Ｍｅ３ＳｉＣ５Ｈ３）Ｆｅ（ＣＯ）２Ｒ〕２（Ｒ：Ｍ     

废水中硫化物的快速分光光度法测定

1　引　　言滴定法和亚甲蓝法是目前广泛使用的硫化物测定法。亚甲蓝法灵敏度高 ,选择性好 ,但反应速度慢 ,重现性较差。本文用Ｋ2 Ｃｒ2 Ｏ7代替Ｆｅ3+,实验结果表明 :在Ｈ2 ＳＯ4 溶液中 ,Ｋ2 Ｃｒ2 Ｏ7+对二乙氨基苯胺 +Ｓ2 -显色反应即刻完成 ,表观摩尔吸收系数为 5 42× 10 4 Ｌ·ｍｏｌ-1·ｃｍ-1,比原乙基蓝法灵敏度提高 40 % ,线性范围为 0～ 0 .6ｍｇ/Ｌ。采用蒸馏分离方法 ,用ＮａＯＨ作吸收液 ,提出了一种适于水样中硫化物测定的快速分光光度法。方法简便快速且检测灵敏度高 ,已用于水和废水中硫化物的测定。2　实验部分2 1　…     

（四甲基二硅撑）双（3－三甲硅基环戊二烯基）－四羰基二铁的反应性

标题化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２／（μ－ＣＯ）_２（Ａ）分子中的Ｆｅ－Ｆｅ键被钠汞齐还原断裂，生成相应的双铁负离子，分别与ＭｅＣＯＣｌ、ＰｈＣＯＣｌ、ＰｈＣＨ_２Ｃｌ、ＣｌＣＨ_２ＣＯＯＣ_２Ｈ_５和Ｐｈ_３ＳｎＣｌ进行亲核取代反应，生成在铁原子上引入相应取代基的产物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２Ｒ］_２（Ｒ：ＭｅＣＯ（１），ＰｈＣＯ（２），ＰｈＣＨ_２（３），ＣＨ_２ＣＯＯＣ_２Ｈ_５（４），Ｐｈ_３Ｓｎ（５），Ｉ（６））。Ａ在氯仿中与碘反应，得到Ｆｅ－Ｆｅ断裂的双铁碘化物，但在苯中与过量碘反应，则得到Ｆｅ－Ｉ－Ｆｅ桥联的离子型化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２Ｉ·Ｉ（７）。化合物６的晶体和分子结构经Ｘ射线衍射测定，６属单斜晶系，Ｐ２１／ｃ空间群，ａ＝１．７２１７（４）ｎｍ，ｂ＝０．７７５３（２）ｎｍ，Ｃ＝１．３６２９（７）ｎｍ，β＝１０３．８０（３）°，Ｖ＝１．７６７（２）ｎｍ３，Ｚ＝４，Ｄｃ＝１．６２９９·ｃｍ－１，最终偏差因子Ｒ＝０．０５４。     

苯二甲酰基桥联铁硫配合物［（μ－RS）Fe_2（CO）_6］_2（μ－OCC_6

通过由Ｆｅ３（ＣＯ）１２、ＲＳＨ和Ｅｔ３Ｎ所形成的［（μ－ＣＯ）（μ－ＲＳ）Ｆｅ２（ＣＯ）６］Ｅｔ３ＮＨ于室温下分别与对或间苯二甲酰氯的原位反应，首次合成６个结构新颖的苯二甲酰基桥联铁硫配合物［（μ－ＲＳ）·Ｆｅ２（ＣＯ）６］２（μ－ｐ－ＯＣＣ６Ｈ４ＣＯ－ｐ－μ）（Ｒ＝Ｅｔ，ｎ－Ｂｕ，ｔ－Ｂｕ）以及［（μ－ＲＳ）Ｆｅ２（ＣＯ）６］２（μ－ｍ－ＯＣＣ６Ｈ４ＣＯ－ｍ－μ）（Ｒ＝ｎ－Ｐｒ，ｎ－Ｂｕ，ｔ－Ｂｕ）。经元素分析、ＩＲ光谱及１ＨＮＭＲ表征了它们的结构，并讨论了产物的生成过程。此外，还提出了合成对苯二甲酰氯的一种新方法。     

Synthesis of [Ag(NH=CMe(2))(2)]ClO(4) and its use as a source of acetimine. 1. Synthesis of the first acetimine rhodium complexes and the first crystal structure of a diacetonamine complex

The reaction of AgClO(4) and NH(3) in acetone gave [Ag(NH=CMe(2))(2)]ClO(4) (1). The reactions of 1 with [RhCl(diolefin)](2) or [RhCl(CO)(2)](2) (2:1) gave the bis(acetimine) complexes [Rh(diolefin)(NH=CMe(2))(2)]ClO(4) [diolefin = 1,5 cyclooctadiene = cod (2), norbornadiene = nbd (3)] or [Rh(CO)(2)(NH=CMe(2))(2)]ClO(4) (4), respectively. Mono(acetimine) complexes [Rh(diolefin)(NH=CMe(2))(PPh(3))]ClO(4) [diolefin = cod (5), nbd (6)] or [RhCl(diolefin)(NH=CMe(2))] [diolefin = cod (7), nbd (8)] were obtained by reacting 2 or 3 with PPh(3) (1:1) or with Me(4)NCl (1:1.1), respectively. The reaction of 4 with PR(3) (R = Ph, To, molar ratio 1:2) led to [Rh(CO)(NH=CMe(2))(PR(3))(2)]ClO(4) [R = Ph (9), C(6)H(4)Me-4 = To (10)] while cis-[Rh(CO)(NH=CMe(2))(2)(PPh(3))]ClO(4) (11) was isolated from the reaction of 1 with [RhCl(CO)(PPh(3))](2) (1:1). The crystal structures of 5 and [Ag[H(2)NC(Me)(2)CH(2)C(O)Me](PTo(3))]ClO(4) (A), a product obtained in a reaction between NH(3), AgClO(4), and PTo(3), have been determined.     

Iron carbonyl sulfides, formaldehyde, and amines condense to give the proposed azadithiolate cofactor of the Fe-only hydrogenases

The azadithiolate (SCH2NHCH2S) cofactor proposed to occur in the Fe-only hydrogenases forms efficiently by the condensation of Fe2(SH)2(CO)6 (1), formaldehyde, and ammonia (as (NH4)2CO3). The resulting Fe2[(SCH2)2NH](CO)6 reacts with Et4NCN to give (Et4N)2[Fe2[(SCH2)2NH](CO)4(CN)2], for which crystallographic characterization confirmed an axial N-H and an elongated C-S bond of 1.858(3) A. Primary amines RNH2 (R = Ph, t-Bu) also participate in the condensation reaction, and Fe3S2(CO)9 can be employed in place of 1. Mechanistically, the Fe2[(SCH2)2NH] moiety is shown to arise via two pathways: (i) via the intermediacy of Fe2[(SCH2OH)2](CO)6, which was detected and shown to react with amines, and (ii) via the reaction of 1 with cyclic imines (CH2)3(NR)3 (R = Ph, Me). The reaction of 1 with (CH2)6N4 (hexamethylenetetramine) gives Fe2[(SCH2)2NH](CO)6. Trace amounts of Fe2[(SCH2)2N-t-Bu](CO)6 arise via the reaction of aqueous FeSO4, formaldehyde, NaSH, and t-BuNH2 under an atmosphere of CO.     

Tautomerization of methyldiazene to formaldehyde-hydrazone in ruthenium and osmium complexes

Mixed-ligand hydrazine complexes [M(CO)(RNHNH2)P4](BPh4)2 (1, 2) [M = Ru, Os; R = H, CH3, C6H5; P = P(OEt)3] with carbonyl and triethyl phosphite were prepared by allowing hydride [MH(CO)P4]BPh4 species to react first with HBF4.Et2O and then with hydrazines. Depending on the nature of the hydrazine ligand, the oxidation of [M(CO)(RNHNH2)P4](BPh4)2 derivatives with Pb(OAc)4 at -30 C gives acetate [M(kappa1-OCOCH3)(CO)P4]BPh4 (3a), phenyldiazene [M(CO)(C6H5N=NH)P4](BPh4)2 (3c, 4c), and methyldiazene [M(CO)(CH3N=NH)P4](BPh4)2 (3b, 4b) derivatives. Methyldiazene complexes 3b and 4b undergo base-catalyzed tautomerization of the CH3N=NH ligand to formaldehyde-hydrazone NH2N=CH2, giving the [M(CO)(NH2N=CH2)P4](BPh4)2 (5, 6) derivatives. Complexes 5 and 6 were characterized spectroscopically and by the X-ray crystal structure determination of the [Ru(CO)(NH2N=CH2)[P(OEt)3]4](BPh4)2 (5) derivative. Acetone-hydrazone [M(CO)[NH2N=C(CH3)2]P4](BPh4)2 (7, 8) complexes were also prepared by allowing hydrazine [M(CO)(NH2NH2)P4](BPh4)2 derivatives to react with acetone.     

固-液相转移催化合成V.醛亚胺的michael加成和羰基加成反应合成α-氨基 酸

报道了在以K~2CO~2为固体碱的固-液相转移催化条件下,用醛亚胺与亲电的 烯烃和醛类化合物进行Michael加成,羰基加成反应,合成了一系列醛亚胺亲核加成产物.并通过水解羰基加成产物制备了一系列丝氨酸衍生物.该法简便,温和,反应时间短,产率高,是合成具有取代基的甘氨酸,丙氨酸和丝氨酸及其酯的一种有用方法.     

Synthesis of acetimino complexes of Pt(II) and Pt(IV) and the first heteronuclear mu-acetimido complexes

The reactions of [Ag(NH=CMe2)2]ClO4 with cis-[PtCl2L2] in a 1:1 molar ratio give cis-[PtCl(NH=CMe2)(PPh3)2]ClO4 (1cis) or cis-[PtCl(NH=CMe2)2(dmso)]ClO4 (2), and in 2:1 molar ratio, they produce [Pt(NH=CMe2)2L2](ClO4)2 [L = PPh3 (3), L2= tbbpy = 4,4'-di-tert-butyl-2,2'-dipyridyl (4)]. Complex 2 reacts with PPh3 (1:2) to give trans-[PtCl(NH=CMe2)(PPh3)2]ClO(4) (1trans). The two-step reaction of cis-[PtCl2(dmso)2], [Au(NH=CMe2)(PPh3)]ClO4, and PPh3 (1:1:1) gives [SP-4-3]-[PtCl(NH=CMe2)(dmso)(PPh3)]ClO4 (5). The reactions of complexes 2 and 4 with PhICl2 give the Pt(IV) derivatives [OC-6-13]-[PtCl3(NH=CMe2)(2)(dmso)]ClO4 (6) and [OC-6-13]-[PtCl2(NH=CMe2)2(dtbbpy)](ClO4)2 (7), respectively. Complexes 1cis and 1trans react with NaH and [AuCl(PPh3)] (1:10:1.2) to give cis- and trans-[PtCl{mu-N(AuPPh3)=CMe2}(PPh3)2]ClO4 (8cis and 8trans), respectively. The crystal structures of 4.0.5Et2O.0.5Me2CO and 6 have been determined; both exhibit pseudosymmetry.     

Urea as a new and cheap nitrogen source for the synthesis of metal nitride clusterfullerenes: the role of decomposed products on the selectivity of fullerenes

By using urea as the new nitrogen source, for the first time, Sc-based metal nitride clusterfullerenes (NCFs), Sc(3)N@C(2n) (2n=80, 78, 70, 68), have been synthesized successfully. The optimum molar ratio of Sc(2)O(3)/CO(NH(2))(2)/C for the synthesis of Sc NCFs is 1:3:15. The yield of Sc(3)N@C(80)(I(h) +D(5h)) per gram of Sc(2)O(3), using CO(NH(2))(2) as the new nitrogen source, was quantitatively compared to those obtained when using the reported nitrogen sources, including N(2), NH(3), and guanidinium thiocyanate. We find that there is a clear difference on the selectivity of Sc-based NCFs within the extract mixture obtained from one rod and accumulative two rods. According to discharging experiments and XRD analysis, we conclude that NH(3) generated in situ from the decomposition of CO(NH(2))(2) is mainly responsible for the formation of Sc-based NCFs when using only one rod, whereas in the second rod CO(NH(2))(2) would decompose into melamine during discharging of the first rod. Thus, the selectivity of fullerenes is clearly dependent on the decomposed product of CO(NH(2))(2). Finally the difference in the decomposition behavior of CO(NH(2))(2) and melamine was studied in detail and a possible decomposition process of CO(NH(2))(2) during discharging was proposed. Accordingly, the difference in the selectivity and yield of Sc NCFs for CO(NH(2))(2) and melamine was interpreted.     

Laser diode photoacoustic detection in the infrared and near infrared spectral ranges

A new technique for high resolution photoacoustic detection based on application of laser diodes has been developed. This method was tested and compared using identical photoacoustic instrumentation (cell and microphone) to study gas absorption in three different spectral regions, namely: the infrared range near 2100 cm(-1), CO and OCS fundamental band absorption; the ranges near 4200 and 4350 cm(-1), CH4, NH3 and N2O overtone and combination band absorption; the near infrared range near 6500 cm(-1), CO, CO2 and NH3 overtone absorption. Several types of diode laser operating at room temperature or at liquid nitrogen temperature were compared. The optimum gas pressures for the maximum sensitivity of the photoacoustic signals were found and the detection limits were estimated for all of the gases studied. The best sensitivity was achieved for NH3 at 100 ppbv. The sensitivity of the developed system was tested on detection of traces of NH3 and CO2 gases from car exhaust.     

Vacuum ultraviolet (VUV) photodecomposition of urea isolated in cryogenic matrix: first detection of isourea

Vacuum ultraviolet (VUV) irradiation at wavelengths of lambda > 160 nm of urea-h4 (NH2CONH2) and urea-d4 (ND2COND2) has been monitored by Fourier transform infrared spectroscopy in argon and xenon matrixes. Several primary photoproducts, such as HNCO:NH3 (isocyanic acid:ammonia), CO:N2H4 (carbon monoxide:hydrazine) molecular complexes, and isourea (H2N(OH)C=NH), which is reported for the first time, were characterized. The assignment of complexes was achieved by co-depositing the pairs of respective species, whereas the isourea identification was based on the comparison between the experimental and theoretical (B3LYP) infrared spectra. Isourea is found in the argon matrix in its most stable (s-Z)-(E) configuration. It is an intermediate in the VUV decomposition process; its dehydration leads to the NH2CN:H2O complex. In the xenon matrix, the photochemistry of urea yields the HNCO:NH3 complex as a major product, whereas the CO:N2H4 complex is observed in trace amounts. The observed differences between the argon and xenon matrixes suggest the crossing between S1 and T1 potential surfaces of urea to be responsible for the formation of the HNCO:NH3 complex. A comparison is also performed with other carboxamides, such as formamide (HCONH2) or acetamide (CH3CONH2).     

Determination of the rate constants for the NH2(X2B1) + NH2(X2B1) and NH2(X2B1) + H Recombination reactions with collision partners CH4, C2H6, CO2, CF4, and SF6 at low pressures and 296 K. Part 2

The recombination rate constants for the reactions NH2(X2B1) + NH2(X2B1) + M → N2H4 + M and NH2(X2B1) + H + M → NH3 + M, where M was CH4, C2H6, CO2, CF4, or SF6, were measured in the same experiment over presseure ranges of 1-20 and 7-20 Torr, respectively, at 296 ± 2 K. The NH2 radical was produced by the 193 nm laser photolysis of NH3. Both NH2 and NH3 were monitored simultaneously following the photolysis laser pulse. High-resolution time-resolved absorption spectroscopy was used to monitor the temporal dependence of both species: NH2 on the (1)2(21) ← (1)3(31) rotational transition of the (0,7,0)A2A1 ← (0,0,0)X2B1 electronic transition near 675 nm and NH3 in the IR on either of the inversion doublets of the qQ3(3) rotational transition of the ν1 fundamental near 2999 nm. The NH2 self-recombination clearly exhibited falloff behavior for the third-body collision partners used in this work. The pressure dependences of the NH2 self-recombination rate constants were fit using Troe’s parametrization scheme, k(inf), k(0), and F(cent), with k(inf) = 7.9 × 10(-11) cm3 molecule(-1) s(-1), the theoretical value calculated by Klippenstein et al. (J. Phys. Chem. A113, 113, 10241). The individual Troe parameters were CH4, k(0)(CH4) = 9.4 × 10(-29) and F(cent)(CH4) = 0.61; C2H6, k(0)(C2H6) = 1.5 × 10(-28) and F(cent)(C2H6) = 0.80; CO2, k(0)(CO2) = 8.6 × 10(-29) and F(cent)(CO2) = 0.66; CF4, k(0)(CF4) = 1.1 × 10(-28) and F(cent)(CF4) = 0.55; and SF6, k(0)(SF6) = 1.9 × 10(-28) and F(cent)(SF6) = 0.52, where the units of k0 are cm6 molecule(-2) s(-1). The NH2 + H + M reaction rate constant was assumed to be in the three-body pressure regime, and the association rate constants were CH4, (6.0 ± 1.8) × 10(-30); C2H6, (1.1 ± 0.41) × 10(-29); CO2, (6.5 ± 1.8) × 10(-30); CF4, (8.3 ± 1.7) × 10(-30); and SF6, (1.4 ± 0.30) × 10(-29), with units cm6 molecule(-1) s,(-1) and the systematic and experimental errors are given at the 2σ confidence level.     

Neighbouring group processes in the deamination of protonated phenylalanine derivatives

The gas-phase fragmentation of protonated phenylalanine and a series of its derivatives (tyrosine, 4-methylphenylalanine, 4-aminophenylalanine, 4-methoxyphenylalanine, 4-tert-butylphenylalanine, 4-fluorophenylalanine, 4-chlorophenylalanine, 4-bromophenylalanine, 4-iodophenylalanine, 4-cyanophenylalanine, 4-nitrophenylalanine, 3-fluorophenylalanine, and 3,4-dichlorophenylalanine) were examined using a combination of low energy CID in a quadrupole ion trap mass spectrometer as well as DFT calculations and RRKM modelling. In particular, the relationship between the electron-donating ability of the substituent and the competitive losses of H2O + CO and NH3 were explored through the application of the Hammett equation. It was found that electron-donating substituents promote the loss of NH3, while electron-withdrawing substituents suppress the loss of NH3 and favour the H2O + CO loss fragmentation channel instead. These observations are consistent with a neighbouring group pathway operating for the loss of NH3. Molecular orbital calculation (at the B3LYP/6-31+G(d,p) level of theory) were also performed for a range of derivatives to compare the relative transition state energy barriers for three competing mechanisms: (i) the combined loss of H2O + CO, which is triggered by an initial intramolecular proton transfer from the ammonium group to hydroxyl OH, followed by the combined loss of H2O and CO to form an immonium ion; (ii) loss of NH3 via an aryl assisted neighbouring group pathway to yield a phenonium ion; (iii) loss of NH3 via a 1,2-hydride migration process, which results in the formation of a benzyl cation. The relative energy barriers for H2O + CO loss remain nearly constant, while that for both NH3 pathways increase as the substituent moves from electron-donating to electron-withdrawing. The relative transition state energy for loss of NH3 via the aryl assisted neighbouring group pathway is always lower than that of the 1,2-hydride migration process. RRKM modelling of the DFT predicted barrier heights suggest that the rate constants for H2O + CO loss are insensitive to the substituent on the ring, while the NH3 loss channels are greatly affected by the substituent. These theoretical results are consistent with the experimental observation of the relative yields of the competing fragmentation channels. Finally, comparisons with published gas phase and condensed phase studies on related systems are made.