[Ir(1,5-COD)(P(C6H5)3)2]BF4 | 38834-40-1

• 英文名称: [Ir(1,5-COD)(P(C6H5)3)2]BF4
• CAS: 38834-40-1
• 化学式: BF₄*C₄₄H₄₂IrP₂
• 分子量: 911.79
• InChiKey: ZMBAYIWFMVLWMW-JXNOXZOESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Ir(1,5-COD)(P(C6H5)3)2]BF4 在 氢气 、 丙酮 作用下， 以 丙酮 为溶剂， 生成 cis,trans-dihydrido(acetone)2bis(triphenylphosphine)iridium(III) tetrafluoroborate
  参考文献：
  名称：

  Alkane dehydrogenation by iridium complexes

  摘要：

  DOI：

  10.1021/ja00365a021
• 作为产物：
  描述：

  cis,trans-dihydrido(acetone)2bis(triphenylphosphine)iridium(III) tetrafluoroborate 、 环辛烷 在 3,3-二甲基-1-丁烯 作用下， 以 1,2-二氯乙烷 为溶剂， 以47%的产率得到[Ir(1,5-COD)(P(C6H5)3)2]BF4
  参考文献：
  名称：

  Alkane dehydrogenation by iridium complexes

  摘要：

  DOI：

  10.1021/ja00365a021
• 作为试剂：
  描述：

  格列本脲 在 超重氢 、 [Ir(1,5-COD)(P(C6H5)3)2]BF4 作用下， 以 二氯甲烷 为溶剂， 反应 16.0h， 生成 3-chloro-N-[2-[4-(cyclohexylcarbamoylsulfamoyl)phenyl]ethyl]-6-methoxy-2-tritiobenzamide
  参考文献：
  名称：

  Direct tritium labeling of multifunctional compounds using organoiridium catalysis

  摘要：

  The tritium exchange labeling of a variety of complex compounds is achieved in the presence of catalyst precursor [(cod)Ir(PPh(3))(2)]BF4 and limited amounts of tritium gas. The regioselectivity of exchange is high and consistent with empirical rules previously observed. High specific activity levels are often achieved, usually with specific aryl C-H bonds. However, remarkably efficient exchange occurs in certain N-alkyl groups. Studies of intermolecular inhibition of catalytic exchange suggest reasons why larger amounts of complex are sometimes required to label complex molecules; nevertheless, significant amounts of label incorporation into substrates can be achieved even stal ting with small amounts of labeling gas.

  DOI：

  10.1002/(sici)1099-1344(199704)39:4<291::aid-jlcr973>3.0.co;2-k

文献信息

• Synthesis and characterisation of some iridium-carbonyl-fluoride complexes. Crystal structures of [IrF(CO){P(C6H4-2-CH3)3}2] and [IrF2(COD)py2][BF4]
  作者：John Fawcett、Duncan A. J. Harding、Eric G. Hope

  DOI：10.1039/c0dt00066c

  日期：——

  Two routes to iridium(III) fluorocomplexes are described. The direct reaction of tetrairidium dodecacarbonyl with elemental fluorine in aHF offers a clean, convenient, large scale route to [IrF3(CO)3]; addition of phosphines to [IrF3(CO)3] in THF affords mer-[IrF3(CO)L2] or [IrF(CO)L2]. Alternatively, cationic [IrF2(COD)L2]+ and [IrF2(CO)2L2]+ (L = phosphine, pyridine; L2 = α-diimine) are accessible

  两条路线 铱（III）描述了氟络合物。的直接反应十二羰基四铱 含氟 高频提供清洁，方便，大规模的[IrF 3（CO）3 ]路线；在[IrF 3（CO）3 ]中添加膦四氢呋喃得到聚体- [IRF 3（CO）L- 2 ]或[IRF（CO）L- 2 ]。或者，阳离子型[IrF 2（COD）L 2 ] +和[IrF 2（CO）2 L 2 ] +（L =膦， 吡啶; L 2 =α-二亚胺）可通过铱（I）前体与二氟化氙。
• Dihydrido olefin and solvento complexes of iridium and the mechanisms of olefin hydrogenation and alkane dehydrogenation
  作者：Robert H. Crabtree、Peter C. Demou、Don Eden、Jean M. Mihelcic、Charles A. Parnell、Jennifer M. Quirk、George E. Morris

  DOI：10.1021/ja00389a018

  日期：1982.12

  generality is discussed. (Ir(cod)L2) A (L = PPh3) reacts with H2 and S (S = solvent) to give the isolable complexes (IrH2S2L2)A (1) in which the displacement order of the M-S groups is H2O = THF < /-BuOH < !-PrOH < Me2CO < EtOH < MeOH < MeCN. The utility of this order in understanding our alkane activation system based on 1 and the effects of S on catalytic hydrogenation are discussed. 1 (S = H2O) reacts

  对催化剂 (Ir(cod)L2)A/CH2 CL2/H2（cod = 1,5-环辛二烯；A = BF4；L = PPh3、PMePh2）进行了均匀性测试，并讨论了它们可能的通用性。(Ir(cod)L2) A (L = PPh3) 与 H2 和 S（S = 溶剂）反应生成可分离的复合物 (IrH2S2L2)A (1)，其中 MS 基团的置换顺序为 H2O = THF < / -BuOH < !-PrOH < Me2CO < EtOH < MeOH < MeCN。讨论了该顺序在理解我们基于 1 的烷烃活化系统中的效用以及 S 对催化氢化的影响。1 (S = ) 在 -80 0C 与烯烃反应生成 (IrH2(Ol)2L2)A (ol = C 2H4, C3Hg) 和 (IrH2(Ol)( )L2 )A (ol = PhCH=CH 2 , C5H8, '-BuCH= )。从逐步催化的角度讨论了它们在加氢中的作用
• Double Geminal C−H Activation and Reversible α-Elimination in 2-Aminopyridine Iridium(III) Complexes:  The Role of Hydrides and Solvent in Flattening the Free Energy Surface
  作者：Eric Clot、Junyi Chen、Dong-Heon Lee、So Young Sung、Leah N. Appelhans、Jack W. Faller、Robert H. Crabtree、Odile Eisenstein

  DOI：10.1021/ja048473j

  日期：2004.7.1

  [H2Ir(OCMe2)2L2]BF4 (1) (L = PPh3), a preferred catalyst for tritiation of pharmaceuticals, reacts with model substrate 2-(dimethylamino)pyridine (py-NMe2; py = 2-pyridyl) to give chelate carbene [H2Ir(py-N(Me)CH=)L2]BF4 (2a) via cyclometalation, H2 loss, and reversible alpha-elimination. Agostic intermediate [H2Ir(py-N(Me)CH2-H)L2]BF4) (4a), seen by NMR, is predicted (DFT(B3PW91) computations) to

  [H2Ir(OCMe2)2L2]BF4 (1) (L = PPh3)，一种优选的药物氚化催化剂，与模型底物 2-（二甲氨基）吡啶（py-NMe2；py = 2-吡啶基）反应生成螯合卡宾[H2Ir(py-N(Me)CH=)L2]BF4 (2a) 通过环金属化、H2 损失和可逆的 α-消除。核磁共振观察到的 Agostic 中间体 [H2Ir(py-N(Me)CH2-H)L2]BF4) (4a) 被预测（DFT（B3PW91）计算）产生 CH 氧化加成形成烷基中间体 [(H) (eta2-H2)Ir(py-N(Me) -)L2]BF4。H2 的损失导致完全表征的烷基 [HIr(OCMe2)(py-N(Me) -)L2]BF4 (3a(Me2CO))，它失去丙酮，通过快速可逆的 α-消除得到亚烷基氢化物 2a。2a 在 d6-丙酮中与过量的 H2 快速反应，以 1:1:1 的比例生成 [
• NMR Studies of Chiral P,S-Chelate Platinum, Rhodium, and Iridium Complexes and the X-ray Structure of a Palladium(II) Allyl Derivative
  作者：Alberto Albinati、Jürgen Eckert、Paul Pregosin、Heinz Rüegger、Renzo Salzmann、Corinna Stössel

  DOI：10.1021/om960823q

  日期：1997.2.1

  Several Rh(I), Ir(III), and Pt(II) complexes of the chiral P,S-bidentate ligand 2 have been prepared and characterized. Detailed two-dimensional NMR studies show that (i) the boat-type chelate ring and the stereogenic sulfur center can invert rapidly at ambient temperature and (ii) the sulfur donor may dissociate, essentially destroying the chiral pocket. The solid-state structure of [Pt(η3-C3H5)(2)]PF6 (3)

  已经制备并表征了手性P，S-二齿配体2的几种Rh（I），Ir（III）和PT（II）配合物。详细的二维NMR研究表明，（i）船型螯合物环和立构硫原子中心可以在环境温度下快速反转，并且（ii）硫供体可能解离，从而基本上破坏了手性口袋。的固态结构[PT（η 3 -C 3 H ^ 5）（2）] PF 6（3）已经确定并示出的硫取代基具有轴向取向。六元螯合物环具有船形构象。如X射线衍射研究显示的3，并通过对Pd类似物4的非相干非弹性中子散射（IINS）测量，得出OH基团远离金属原子。
• Synthesis and Catalytic Applications of Chiral Hydridoiridium(III) Complexes with Diamine/Bis(monophosphane) and Diamine/Diphosphane Coordination
  作者：Lutz Dahlenburg、Ralf Menzel、Frank W. Heinemann

  DOI：10.1002/ejic.200700380

  日期：2007.9

  The P 2 /N 2 -coordinated cis-dihydridoiridium(III) chelate complexes (OC-6-13)-[IrH2(H2NnNH2)(PR3) 2 ]BF 4 [PR 3 = PPh 3 , H 2 N∩NH 2 = 1,2-(H 2 N) 2 C 6 H 4 (la); (1R,2R)-(H 2 N) 2 C 6 H 10 R,R)-dach} (1b); (R)-2,2'-diamino-1,1'-binaphthyl (R)-dabin) (1c); PR 3 = PiPr 3 , H 2 NnNH 2 = (R,R)-dach (2a), (R)-dabin (2b); PR 3 = PCy 3 , H 2 N∩NH 2 = (R)-dabin (3)] were obtained by treating the respective

  P 2 /N 2 配位顺式二氢铱(III)螯合物(OC-6-13)-[IrH2(H2NnNH2)(PR3) 2 ]BF 4 [PR 3 = PPh 3 , H 2 N∩NH 2 = 1,2-(H 2 N) 2 C 6 H 4 (la)；(1R,2R)-(H 2 N) 2 C 6 H 10 R,R)-dach} (1b)；(R)-2,2'-二氨基-1,1'-联萘(R)-dabin) (1c)；PR 3 = PiPr 3 ，H 2 NnNH 2 = (R,R)-dach (2a), (R)-dabin (2b)；PR 3 = PCy 3 , H 2 N∩NH 2 = (R)-dabin (3)] 通过用不稳定的前体如[IrH2(OCMe2)2(PPh3)2]BF4，[ η 4 -1,5-C 8 H 12 )Ir(PPh 3 ) 2 ]BF 4 ，或[IrH 5 (PR 3 ) 2 ]/HBF