离子液体Zn[CO(NH2)2]3Cl2介质中二肽催化醛的不对称α-氯代反应

以二肽Pro-Trp为催化剂,2,3,4,5,6,6-六氯-2,4-环己二烯-1-酮为氯化剂,离子液体Zn[CO(NH₂)₂]₃Cl₂为溶剂,在N-甲基吗啉(NMM)存在下,各种醛能够高收率、较高立体选择性地完成羰基α-卤代反应,目标产物的产率可达到95%,对映选择性可达92%ee。 该方法具有操作简便、离子液体和催化剂可重复使用的优点。     

离子液体介质中钌纳米粒子催化苯乙酮及其衍生物的不对称加氢反应

采用水溶性三(间-磺酸钠苯基)膦(TPPTS)作稳定剂, 在离子液体1-丁基-3-甲基-咪唑四氟硼酸盐([BMIM]BF4)或1-丁基-3-甲基-咪唑对甲基苯磺酸盐([BMIM][p-CH3C6H4SO3])介质中用氢气还原RuCl3·3H2O, 得到钌纳米粒子. 将此钌纳米粒子与(1S, 2S)-1,2-二苯基乙二胺(简称(1S, 2S)-DPEN)、KOH在离子液体/异丙醇介质中原位生成一种不对称加氢催化剂, 用于催化苯乙酮及其衍生物的不对称加氢反应. 实验结果表明, 离子液体介质中的纳米钌催化剂体系具有良好的催化活性和对映选择性. 在优化反应条件下, 催化苯乙酮获得了100%的转化率和79.1%的对映选择性. 并且产物经正己烷萃取后, 含有钌纳米粒子的离子液体可以循环使用.     

碱性离子液体催化甘油合成1,2-甘油碳酸酯(英)

以离子液体为催化剂,在无溶剂体系中,考察了生物质平台化合物甘油转化1,2-甘油碳酸酯的反应.与酸性离子液体和常用无机碱性催化剂相比,碱性离子液体咪唑基1-丁基-3-甲基咪唑([Bmim]Im)、氢氧化1-丁基-3-甲基咪唑([Bmim]OH)、咪唑基1-烯丙基-3-甲基咪唑([Amim]Im)、氢氧化1-烯丙基-3-甲基咪唑([Amim]OH)在甘油与碳酸二甲酯的酯交换反应中表现出优异的活性.其中,以[Bmim]Im离子液体为催化剂时甘油转化率为98.4%和甘油碳酸酯选择性接近100%.另外,该离子液体可以回收重复利用3次后甘油转化率仍可达92%,甘油碳酸酯选择性可近100%.此碱性离子液体催化方法具有反应结果较好、产物分离简单、条件温和以及环境友好等特点.     

高对映选择性的有机催化的硝基烷烃对N-Boc靛红亚胺的不对称aza-Henry反应

研究实现了高对映选择性的硝基烷烃对N-Boc靛红亚胺1的不对称aza-Henry反应,来构建胺基季碳氧化吲哚. 发现在金鸡纳碱衍生的叔胺-酚羟基双功能催化剂C5的作用下,10种不同取代的N-Boc靛红亚胺与硝基甲烷的反应均能顺利进行,以66%～91%的对映选择性得到目标产物,产物的绝对构型通过X-ray单晶衍射加以确定. 硝基乙烷和硝基丙烷也能高对映选择性地参与反应,但非对映选择性不佳.     

离子液体-乙腈混合溶剂中电催化CO2与甲醇合成碳酸二甲酯

常温常压下分别在离子液体 1-丁基-3-甲基咪唑四氟硼酸盐([bmim]BF4)-MeCN混合溶剂和纯MeCN溶剂中研究了CO2在Cu电极上的循环伏安行为. 结果表明, CO2均发生不可逆还原反应生成CO-2. 与纯MeCN溶剂相比,在混合溶剂中CO2还原峰电位均有正移. 这表明溶剂中的咪唑型离子液体对活化CO2有催化作用. 在混合溶剂中,以CO2和MeOH为原料合成碳酸二甲酯(DMC), 考察了[bmim]BF4/MeCN体积比、工作电极材料、 MeOH浓度和电解电位等对DMC产物收率的影响. 与其他DMC合成方法相比,本法反应条件温和、设备简单、合成产物收率较高. 在优化的条件下, DMC产物收率可达79.6%. 并提出了合成DMC可能的反应机理.     

水相中RuCl2(TPPTS)2-(S,S)-DPENDS催化苄叉丙酮的不对称加氢反应

 将水溶性手性二胺 (S,S)-1,2-二苯基乙二胺二磺酸钠 ((S,S)-DPENDS) 与钌膦配合物 ([RuCl2(TPPTS)2]2) 原位生成的催化剂用于催化水相中苄叉丙酮的不对称加氢反应. 在优化条件下, 羰基加氢产物 4-苯基-3-丁烯-2-醇的选择性可达 96.0%, 对映选择性可达 71.2%. 经正己烷简单萃取后即可实现催化剂与加氢产物的分离, 循环使用 5 次后, 目标产物 4-苯基-3-丁烯-2-醇选择性和对映选择性没有明显下降.     

氯固相合成Ti-ZSM-5催化苯乙烯环氧化对映选择性 的研究

用TiCl~4气固相同晶取代法制得的Ti-ZSM-5作催化剂。研究了以H~2O~2为氧化剂氧化苯乙烯生成环氧苯乙烷的对映选择性,发现生成的环氧苯乙烷主要以R构型为主。考察了反应时间,反应温度,催化剂Ti-ZSM-5以及氧化剂[w(H~2O~2)=30%]的用量等反应条件对苯乙烯环氧化反应对映性的影响。结果表明,反应温度是影响环氧化反应对映选择性的重要因素,降低反应温度有利于提高对映选择性(ee),当反应温度≤40℃时,ee值可达100%;而反应时间,催化剂及氧化剂[w(H~2O~2)=30%]用量对环氧化反应的对映选择性几乎没有影响。     

酸性离子液体高选择性催化合成2,6-二甲基萘

研究了三乙胺氯铝酸盐(Et3NHCl-AlCl3)类离子液体催化剂的酸性及反应条件对1,2,4,5-四甲基苯与2-甲基萘转移烷基化合成2,6-二甲基萘(2,6-DMN)反应的影响规律.结果表明,通过调节Et3NHCl-AlCl3离子液体的酸强度和优化反应温度及反应时间等工艺条件可以高选择性地制备2,6-DMN.以Et3NHCl-AlCl3(x(AlCl3)=0.71)为催化剂,以环己烷为溶剂,在2-甲基萘∶四甲基苯摩尔比为1∶1和20℃的条件下反应6h,2-甲基萘的转化率可达48.8%,DMN的选择性和2,6-DMN占DMN的摩尔百分比分别达到81.2%和52.4%,2,6-DMN的收率可达20.8%.特别需要指出的是,在此优化条件下反应2h,2-甲基萘的转化率为3.7%时,2,6-DMN占DMN的摩尔百分比达到100%.以混合甲基萘和萘为转移烷基化反应原料时也高选择性地得到了2,6-DMN.对Et3NHCl-AlCl3的循环使用性能进行了考察,并分析了失活原因.     

一个新的Cu(II)-二胺配合物催化的Henry反应

研究了L-脯氨酸制得的C2-对称二胺,与醋酸铜形成新的配合物,催化各种醛与硝基烷烃间的Henry反应。 考察了反应温度、溶剂和催化剂用量对收率和反应速率的影响。 研究结果表明,在室温下,以乙醇作为反应溶剂时,摩尔分数10%的二胺醋酸铜配合物能够有效地催化醛与硝基甲烷反应,生成相应的β-硝基醇,收率为60%~92%。 醛与硝基乙烷的Henry反应产物具有非对映立体选择性。 芳香醛参与Henry反应产物的非对映选择性高达24∶1,但脂肪醛为底物时,此催化剂对Henry反应的非对映选择性不明显。     

氯固相合成Ti-ZSM-5催化苯乙烯环氧化对映选择性 的研究

用TiCl~4气固相同晶取代法制得的Ti-ZSM-5作催化剂。研究了以H~2O~2为氧化剂氧化苯乙烯生成环氧苯乙烷的对映选择性,发现生成的环氧苯乙烷主要以R构型为主。考察了反应时间,反应温度,催化剂Ti-ZSM-5以及氧化剂[w(H~2O~2)=30%]的用量等反应条件对苯乙烯环氧化反应对映性的影响。结果表明,反应温度是影响环氧化反应对映选择性的重要因素,降低反应温度有利于提高对映选择性(ee),当反应温度≤40℃时,ee值可达100%;而反应时间,催化剂及氧化剂[w(H~2O~2)=30%]用量对环氧化反应的对映选择性几乎没有影响。     

A new route to coordination complexes of nitroxyl (HN=O) via insertion reactions of nitrosonium triflate with transition-metal hydrides

Nitrosonium triflate reacts with cold methylene chloride solutions of mer,trans-ReH(CO)3(PPh3)2 (1) with 1,1-insertion of NO+ into the Re-H bond to give the orange nitroxyl complex [mer,trans-Re(NH=O)(CO)3(PPh3)2][SO3CF3] (3) in 86% isolated yield. Use of [NO][PF6] or [NO][BF4] gives analogous insertion products at low temperature, which decompose on warning to ambient temperature to the fluoride complex mer,trans-ReF(CO)3(PPh3)2 (4). A related 1,1-insertion is observed in the reaction of 1 with [PhN2][PF6] in acetone that affords the yellow-orange phenyldiazene salt [mer,trans-Re(NH=NPh)(CO)3(PPh3)2][PF6] (2), which has been characterized by X-ray crystallographic methods. The methyl derivative mer,trans-Re(CH3)(CO)3(PPh3)2 (5) also undergoes a 1,1-insertion reaction with [NO][SO3CF3] to give the nitrosomethane adduct [mer,trans-Re{N(CH3)=O}(CO)3(PPh3)2][SO3CF3] (6) as red crystals in 75% yield. The nitroxyl complex [cis,trans-OsBr(NH=O)(CO)2(PPh3)2][SO3CF3] (8) can be similarly prepared as orange crystals in 52% yield by reaction of cis,trans-OsHBr(CO)2(PPh3)2 (7) with [NO][SO3CF3] in cold methylene chloride solution.     

Key factors determining the course of methyl iodide oxidative addition to diamidonaphthalene-bridged diiridium(I) and dirhodium(I) complexes

The course of methyl iodide oxidative addition to various nucleophilic complexes, [Ir2(mu-1,8-(NH)2naphth)(CO)2(PiPr3)2] (1), [IrRh(mu-1,8-(NH)2naphth)(CO)2(PiPr3)2] (2), and [Rh2(mu-1,8-(NH)2naphth)(CO)2(PR3)2] (R = iPr, 3; Ph, 4; p-tolyl, 5; Me, 6), has been investigated. The CH3I addition to complex 1 readily affords the diiridium(II) complex [Ir2(mu-1,8-(NH)2naphth)I(CH3)(CO)2(PiPr3)2] (7), which undergoes slow rearrangement to give a thermodynamically stable stereoisomer, 8. The reaction of the Ir-Rh complex 2 gives the ionic compound [IrRh(mu-1,8-(NH)2naphth)(CH3)(CO)2(PiPr3)2]I (10). The dirhodium compounds, 3-5, undergo one-center additions to yield acyl complexes of the formula (Rh2(mu-1,8-(NH)2naphth)I(COCH3)(CO)(PR3)2] (R = iPr, 12; Ph, 13; p-tolyl, 14). The structure of 12 has been determined by X-ray diffraction. Further reactions of these Rh(III)-Rh(I) acyl derivatives with CH3I are productive only for the p-tolylphosphine derivative, which affords the bis-acyl complex [Rh2(mu-1,8-(NH)2naphth)(CH3CO)2I2(P(p-tolyl)3)2] (15). The reaction of the PMe3 derivative, 6, allows the isolation of the bis-methyl complex [Rh2(mu-1,8-(NH)2naphth)(mu-I)(CH3)2(CO)2(PMe3)2]I (16a), which emanates from a double one-center addition. Upon reaction with methyl triflate, the starting materials, 1, 2, 3, and 6, give the isostructural cationic methyl complexes 9, 11, 17, and 18, respectively. The behavior of these cationic methyl compounds toward CH3I, CH3OSO2CF3, and tetrabutylamonium iodide is consistent with the role of these species as intermediates in the SN2 addition of CH3I. Compounds 18 and 17 react with an excess of methyl triflate to give [Rh2(mu-1,8-(NH)2naphth)(mu-OSO2CF3)(CH3)2(CO)2(PMe3)2][CF3SO3] (19) and [Rh2(mu-1,8-(NH)2naphth)(OSO2CF3)(COCH3)(CH3)(CO)(PiPr3)2][CF3SO3] (20), respectively. Upon treatment with acetonitrile, complexes 17 and 18 give the isostructural cationic acyl complexes [Rh2(mu-1,8-(NH)2naphth)(COCH3)(NCCH3)(CO)(PR3)2][CF3SO3] (R = iPr, 21; Me, 22). A kinetic study of the reaction leading to 21 shows that formation of these complexes involves a slow insertion step followed by the fast coordination of the acetonitrile. The variety of reactions found in this system can be rationalized in terms of three alternative reaction pathways, which are determined by the effectiveness of the interactions between the two metal centers of the dinuclear complex and by the steric constraints due to the phosphine ligands.     

Atmospheric chemistry of CH3CHF2 (HFC-152a): kinetics, mechanisms, and products of Cl atom- and OH radical-initiated oxidation in the presence and absence of NO(x)

Smog chamber/Fourier transform infrared (FTIR) and laser-induced fluorescence (LIF) spectroscopic techniques were used to study the atmospheric degradation of CH3CHF2. The kinetics and products of the Cl(2P(3/2)) (denoted Cl) atom- and the OH radical-initiated oxidation of CH3CHF2 in 700 Torr of air or N2; diluents at 295 +/- 2 K were studied using smog chamber/FTIR techniques. Relative rate methods were used to measure k(Cl + CH3CHF2) = (2.37 +/- 0.31) x 10(-13) and k(OH + CH3CHF2) = (3.08 +/- 0.62) x 10(-14) cm3 molecule(-1) s(-1). Reaction with Cl atoms gives CH3CF2 radicals in a yield of 99.2 +/- 0.1% and CH2CHF2 radicals in a yield of 0.8 +/- 0.1%. Reaction with OH radicals gives CH3CF2 radicals in a yield >75% and CH2CHF2 radicals in a yield <25%. Absolute rate data for the Cl reaction were measured using quantum-state selective LIF detection of Cl(2P(j)) atoms under pseudo-first-order conditions. The rate constant k(Cl + CH3CHF2) was determined to be (2.54 +/- 0.25) x 10(-13) cm3 molecule(-1) s(-1) by the LIF technique, in good agreement with the relative rate results. The removal rate of spin-orbit excited-state Cl(2P(1/2)) (denoted Cl) in collisions with CH3CHF2 was determined to be k(Cl + CH3CHF2) = (2.21 +/- 0.22) x 10(-10) cm3 molecule(-1) s(-1). The atmospheric photooxidation products were examined in the presence and absence of NO(x). In the absence of NO(x)(), the Cl atom-initiated oxidation of CH3CHF2 in air leads to formation of COF2 in a molar yield of 97 +/- 5%. In the presence of NO(x), the observed oxidation products include COF2 and CH3COF. As [NO] increases, the yield of COF2 decreases while the yield of CH3COF increases, reflecting a competition for CH3CF2O radicals. The simplest explanation for the observed dependence of the CH3COF yield on [NO(x)] is that the atmospheric degradation of CH3CF2H proceeds via OH radical attack to give CH3CF2 radicals which add O2 to give CH3CF2O2 radicals. Reaction of CH3CF2O2 radicals with NO gives a substantial fraction of chemically activated alkoxy radicals, [CH3CF2O]. In 1 atm of air, approximately 30% of the alkoxy radicals produced in the CH3CF2O2 + NO reaction possess sufficient internal excitation to undergo "prompt" (rate >10(10) s(-1)) decomposition to give CH3 radicals and COF2. The remaining approximately 70% become thermalized, CH3CF2O, and undergo decomposition more slowly at a rate of approximately 2 x 10(3) s(-1). At high concentrations (>50 mTorr), NO(x) is an efficient scavenger for CH3CF2O radicals leading to the formation of CH3COF and FNO.     

Heteropolynuclear complexes with the ligand Ph2PCH2SPh: theoretical evidence for metallophilic Au-M attractions

Addition of two equivalents of diphenylthiomethylphosphine (PPh2-CH2SPh) to the starting materials [Au(tht)2]A (tht = tetrahydrothiophene), AgCF3SO3, or [Cu(CH3CN)4]CF3SO3 produces the mononuclear derivatives [M(PPh2CH2SPh)2]A (M = Au, A = CF3SO3 (1a); M = Au, A = ClO4 (1b); M = Ag, A = CF3SO3 (4); M = Cu, A = CF3SO3 (5)) which are able to form the heterodinuclear complexes [AuM'(PPh2CH2SPh)2](CF3SO3)2 (M' = Ag (2), Cu (3)) with a P-Au-P environment. If the starting gold complex is [Au(C6F5)(tht)], reaction with the phosphine produces [Au(C6F5)-(PPh2CH2SPh)] (6) from which, by reaction with AgCF3SO3 or [Cu(CH3CN)4]CF3SO3, the "snake"-type linear complexes [Au2M(C6F5)2-(PPh2CH2SPh)2]CF3SO3 (M = Ag (7), Cu (8)) are obtained. If the silver starting complex is AgCF3CO2, reaction in a 1:1 ratio gives the tetranuclear complex [Au2Ag2(C6F5)2(PPh2CH2SPh)2-(CF3CO2)2] (9). When the molar ratio is 1:2 the trinuclear complex [AuAg2(C6F5) (CF3CO2)2(PPh2CH2SPh)] (10) is obtained. According to ab initio calculations, the presence of only one gold atom is enough to induce metallophilic attractions in the group congeners, and this effect can be modulated depending on the gold ligand.     

Topological variations of the PDP ligand and its prospects in molybdenum(0) dearomatization agents

The compounds fac-(κ(3)-PDP)Mo(CO)(3) {1; PDP = 2-[[2-(1-(pyridin-2-ylmethyl)pyrrolidin-2-yl)pyrrolidin-1-yl]methyl]pyridine}, [(cis-β-PDP)Mo(NO)(CO)]PF(6) ([cis-β-3]PF(6)), [(cis-α-PDP)Mo(NO)(CO)]PF(6) ([cis-α-3]PF(6)), [(cis-α-PDP)Mo(NO)Br]PF(6) ([4]PF(6)), [(trans-PDP)Cu](BF(4))(2)·CH(3)CN ([5](BF(4))(2)·CH(3)CN), and [(trans-PDP)Cu](OSO(2)CF(3))(2) ([5](OSO(2)CF(3))(2)) have been synthesized and structurally characterized by single-crystal X-ray diffraction. These are the first reported complexes of PDP on metal centers other than iron(II). The observed configurations indicate a broader range of accessible PDP topologies than has been reported. The {(cis-α-PDP)Mo(NO)}(+) fragment is found to be less π-basic than the dearomatizing {Tp(MeIm)Mo(NO)} fragment [Tp = hydridotris(1-pyrazolyl)borato; MeIm = 1-methylimidazole].     

UV absorption cross sections between 230 and 350 nm and pressure dependence of the photolysis quantum yield at 308 nm of CF3CH2CHO

Ultraviolet (UV) absorption cross sections of CF(3)CH(2)CHO were determined between 230 and 350 nm by gas-phase UV spectroscopy. The forbidden n → π* transition was characterized as a function of temperature (269-323 K). In addition, the photochemical degradation of CF(3)CH(2)CHO was investigated at 308 nm. The possible photolysis channels are: CF(3)CH(2) + HCO , CF(3)CH(3) + CO , and CF(3)CH(2)CO + H . Photolysis quantum yields of CF(3)CH(2)CHO at 308 nm, Φ(λ=308nm), were measured as a function of pressure (25-760 Torr of synthetic air). The pressure dependence of Φ(λ=308nm) can be expressed as the following Stern-Volmer equation: 1/Φ(λ=308nm) = (4.65 ± 0.56) + (1.51 ± 0.04) × 10(-18) [M] ([M] in molecule cm(-3)). Using the absorption cross sections and the photolysis quantum yields reported here, the photolysis rate coefficient of this fluorinated aldehyde throughout the troposphere was estimated. This calculation shows that tropospheric photolysis of CF(3)CH(2)CHO is competitive with the removal initiated by OH radicals at low altitudes, but it can be the major degradation route at higher altitudes. Photodegradation products (CO, HC(O)OH, CF(3)CHO, CF(3)CH(2)OH, and F(2)CO) were identified and also quantified by Fourier transform infrared spectroscopy. CF(3)CH(2)C(O)OH was identified as an end-product as a result of the chemistry involving CF(3)CH(2)CO radicals formed in the OH + CF(3)CH(2)CHO reaction. In the presence of an OH-scavenger (cyclohexane), CF(3)CH(2)C(O)OH was not detected, indicating that channel (R1c) is negligible. Based on a proposed mechanism, our results provide strong evidences of the significant participation of the radical-forming channel (R1a).     

Stereocontrol in alkyne cyclocarbonylation reactions promoted by a bioxazoline palladium(II) complex

Insertion of 1,2-disubstituted alkynes into [Pd(CH3)(CO)(BIOX)]+[B{3,5-(CF3)2C6H3}4]- (1), where BIOX=(4S,4'S)-(-)-4,4',5,5'-tetrahydro-4,4'-bis(1-methylethyl)-2,2'-bioxazole, leads to the formation of five-membered palladacycles, which, by reaction with carbon monoxide, produce a mixture of two diastereomeric forms of a palladium complex containing an eta3-allylic gamma-lactone ligand. On leaving the mixture in solution, one isomer was converted into the other, reaching a diastereomeric excess of up to 94 %. The steric and electronic factors responsible for the epimerization process were investigated by theoretical methods. Cleavage of the eta3-allyl--palladium bond by nucleophiles allowed highly substituted chiral butenolides to be synthesized in good enantiomeric excess.     

Synthesis and reactivity of fluorinated ferracarborane anions

The ferracarborane [N(PPh3)2][6,6,6,10,10,10-(CO)6-closo-6,10,1-Fe2CB7H8] reacts in CH2Cl2 with 3 molar equivalents of Ag[PF6] to yield the trifluoro-substituted species [N(PPh3)2][7,8,9-F3-6,6,6,10,10,10-(CO)6-closo-6,10,1-Fe2CB7H5]. Compound undergoes structural rearrangement in toluene at reflux temperatures, forming [N(PPh3)2][8,9,10-F3-6,6,6,7,7,7-(CO)6-closo-6,7,1-Fe2CB7H5]. Alternatively, reaction of either or with a 10-fold excess of Ag[PF6] in CH2Cl2 forms two species: namely, [N(PPh3)2][2,7,9,10-F4-6,6,6,8,8,8-(CO)6-closo-6,8,1-Fe2CB7H4], in which one further B-F substitution has occurred and the {Fe2CB7} cluster core has rearranged, plus a mono-iron co-product, [N(PPh3)2][3,8,9-F3-7,7,7-(CO)3-closo-7,1-FeCB7H5] that is formed by polyhedral contraction. Treatment of with [NO][BF4] in CH2Cl2 results in CO substitution at the 4-connected iron vertex [Fe10], producing the zwitterionic complex [7,8,9-F3-6,6,6,10,10-(CO)5-10-NO-closo-6,10,1-Fe2CB7H5]. Addition of Me3NO to a mixture of and PEt3 in CH2Cl2 also results in CO substitution, forming the isomeric species [N(PPh3)2][7,8,9-F3-6,6,m,10,10-(CO)5-n-PEt3-closo-6,10,1-Fe2CB7H5] [m=6, n=10; m=10, n=6] in a 5:1 ratio. Treatment of with [NO][BF4] and then CNBut in CH2Cl2 allows further, successive CO substitution at Fe10 to yield first a neutral, zwitterionic complex [7,8,9-F3-6,6,6,10-(CO)4-10-NO-10-PEt3-closo-6,10,1-Fe2CB7H5] and then [7,8,9-F3-6,6,6-(CO)3-10-CNBut-10-NO-10-PEt3-closo-6,10,1-Fe2CB7H5]. The molecular structures of compounds and have been established by X-ray diffraction.     

1,3-二碘六氟丙烷的电子转移反应

在四醋酸铅的催化下,二氟二碘甲烷(CF2I2,1)与四氟乙烯加成生成1,3-二碘六氟丙烷(ICF2CF2CF2I,3).3与烯烃、炔烃和丙二酸二乙酯阴离子发生电子转移反应。     

The bridged binding mode as a new, versatile template for the selective activation of carbon-fluorine bonds in fluoroolefins: activation of trifluoroethylene

We report the selective activation of carbon-fluorine bonds in trifluoroethylene using the diiridium complex [Ir(2)(CH(3))(CO)(2)(dppm)(2)][OTf] (1). Coordination of trifluoroethylene in a bridging position between the two metals in 1 results in facile fluoride ion loss in three different ways. Attack by strong fluorophiles such as Me(3)SiOTf and HOTf results in F(-) removal from one of the geminal fluorines to give the cis-difluorovinyl-bridged product [Ir(2)(CH(3))(OTf)(CO)(2)(μ-κ(1):η(2)-C(F)═CFH)(dppm)(2)][OTf]. A second activation can also be accomplished by addition of excess Me(3)SiOTf to give the fluorovinylidene-bridged product [Ir(2)(CH(3))(OTf)(CO)(2)(μ-C(2)FH)(dppm)(2)][OTf](2). Interestingly, activation of the trifluoroethylene-bridged precursor by water also occurs, yielding [Ir(2)(CH(3))(CO)(2)(κ(1)-C(H)═CF(2))(μ-OH)(dppm)(2)][OTf], in which the lone vicinal fluorine is removed, leaving a geminal arrangement of fluorines in the product. A [1,2]-fluoride shift can also be induced in the trifluoroethylene-bridged precursor upon the addition of CO to give the 2,2,2-trifluoroethylidene-bridged product [Ir(2)(CH(3))(CO)(3)(μ-C(H)CF(3))(dppm)(2)][CF(3)SO(3)]. Addition of hydrogen to the cis-difluorovinyl-bridged product results in the quantitative elimination of cis-difluoroethylene, while its reaction with CO yields a mixture of cis-difluoropropene and 2,3-difluoropropene by reductive elimination of the methyl and difluorovinyl groups with an accompanying isomerization in the case of the second product. Finally, protonation of the 2,2,2-trifluoroethylidene-bridged product liberates 1,1,1-trifluoroethane, in which one hydrogen (H(+)) is from the acid while the other hydrogen (H(-)) is derived from activation of the methyl group.