tricyclohexylphosphonium tetraphenylborate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: tricyclohexylphosphonium tetraphenylborate
• 英文别名: tetraphenylboranuide;tricyclohexylphosphanium
• 化学式: C₁₈H₃₄P*C₂₄H₂₀B
• 分子量: 600.676
• InChiKey: OBOBNHQUEGFKOA-UHFFFAOYSA-O

计算性质

• 辛醇/水分配系数(LogP)：
  9.26
• 重原子数：
  44
• 可旋转键数：
  7
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  、 tricyclohexylphosphonium tetraphenylborate 以 氘代丙酮 为溶剂， 生成
  参考文献：
  名称：

  Effect of the Ligand and Metal on the pKa Values of the Dihydrogen Ligand in the Series of Complexes [M(H2)H(L)2]+, M = Fe, Ru, Os, Containing Isosteric Ditertiaryphosphine Ligands, L

  摘要：

  The new dihydrogen complexes trans-[MH(H-2)L(2)]BF4, L = P(C6H4-4-R)(2)CH2CH2P(C6H4-4-R)(2), R = CF3, M = Fe, Ru, and Os, R = CH3, M = Fe, R = OMe, M = Ru, are prepared by reaction of the dihydride complexes MH(2)L(2) With HBF4. The H-H bond length of the spinning H-2 ligand does not change significantly as a function of R (from CF3 to CH3 when M = Fe and from CF3 to OCH3 for M = Ru) according to H-1 NMR T-1 and (1)J(HD) measurements while there is a lengthening for the Os complexes. The rate constants for H atom exchange (reflecting the ease of homolytic splitting of H-2) increase with the increasing donor ability of R for a given metal as do the pK(a) values (reflecting a decrease in ease of heterolytic splitting). The electrochemical properties of some complexes MH(Cl)L(2) and MH(2)L(2) are reported. As expected H-2 acidity decreases as the parent hydride becomes easier to oxidize with this change in R (same M). The trend in dihydrogen pK(a) values as a function of the metal, Fe < Os < Ru, is distinctively different to the trend in pK(a) values of the dihydride complexes M(H)(2)(CO)(4), Fe < Ru < Os, and [M(C5H5)(H)(2)(PPh(3))(2)](+), Ru < Os, The high H-H bond energy of the RU(2+) complexes trans-[RuH(H-2)L(2)]BF4 is probably the reason why they are less acidic than corresponding Os2+ complexes. A consideration of the pK(a) values correctly indicated that a RuH(2)L(2)/[RuH(H-2)L(2)](+) mixture would be more effective at H/D exchange between D-2 and HO(t)Bu than the dihydrogen complex alone.

  DOI：

  10.1021/ja00087a024
• 作为产物：
  描述：

  (HP(n-Bu)3)(BPh4) 、 三环己基膦 以 四氢呋喃 为溶剂， 生成 三丁基膦 、 tricyclohexylphosphonium tetraphenylborate
  参考文献：
  名称：

  An Acidity Scale for Phosphorus-Containing Compounds Including Metal Hydrides and Dihydrogen Complexes in THF:  Toward the Unification of Acidity Scales

  摘要：

  More than 70 equilibrium constants K between acids and bases, mainly phosphine derivatives, have been measured in tetrahydrofuran (THF) at 20 degrees C by H-1 and/or P-31 NMR. The acids were chosen or newly synthesized in order to cover the, wide pK(a)(THF) range of 5-41 versus the anchor compound [HPCy3]BPh4 at 9.7. These pK(alpha)(THF) values-are approximations to absolute, free ion pK(a)(THF) and are obtained by crudely correcting the observed K for 1:1 ion-pairing effects by use of the Fuoss equation. The acid/base compounds include 14 phosphonium/phosphine couples, 17 cationic hydride/neutral hydride couples, 9 neutral polyhydride/anionic hydride couples, 14 dihydrogen/hydride couples, and 4 other nitrogen- and phosphorus-based acids. The effects on pK(alpha) of the:counterions BAr'(-)(4) and BF4- vs BPh4- and [K(2,2,2-crypt)](+) versus [K(18-crown-6)](+) are found to be minor after correcting for differences in inter-ion distances in the ion-pairs involved. Correlations with nu(M-H) noted here for the first time suggest that destabilization of M-H bonding in the conjugate base hydride is an important contributor to hydride acidity, It appears that Re-H bonding in the anions [ReH6(PR3)(2)](-) is greatly weakened by small increases in the basicity of PR3, resulting in a large increase in the pK(alpha) of the conjugate acid ReH7(PR3)(2) Correlations with other scales allow an estimate of the pK(alpha)(THF) values of more than 1000 inorganic and organic acids, 20 carbonyl hydride complexes, 46 cationic hydrides complexes, and dihydrogen gas. Therefore, many new acid-base reactions can be predicted and known reactions explained. THF, with its low dielectric constant, disfavors the ionization of neutral acids KA over HB+, and therefore separate lines are found for pK(alpha)(THF)(HA) and pK(alpha)(THF)(HB+) when plotted against pK(a)(DMSO) or pK(a)(MeCN). The crystal structure of [Re(H)(2)(PMe3)(5)]BPh4 is reported.

  DOI：

  10.1021/ja994428d

文献信息

• Process for producing phosponium borate compound, novel phosphonium borate compound, and method of using the same
  申请人：Masaoka Shin

  公开号：US20070098616A1

  公开（公告）日：2007-05-03

  The invention relates to a phosphonium borate compound represented by Formula (I) (hereinafter, the compound (I)). The invention has objects of providing (A) a novel process whereby the compound is produced safely on an industrial scale, by simple reaction operations and in a high yield; (B) a novel compound that is easily handled; and (C) novel use as catalyst. Formula (I): (R 1 )(R 2 )(R 3 )PH.BAr 4 (I) wherein R 1 , R 2 , R 3 and Ar are as defined in the specification. The process (A) includes reacting a phosphine with a) HCl or b) H 2 SO 4 to produce a) a hydrochloride or b) a sulfate; and reacting the salt with a tetraarylborate compound. The compound (B) has for example a secondary or tertiary alkyl group as R 1 and is easily handled in air without special attention. The use (C) is characterized in that the compound (I) is used instead of an unstable phosphine compound of a transition metal complex catalyst for catalyzing C—C bond, C—N bond and C—O bond forming reactions and the compound produces an effect that is equal to that achieved by the transition metal complex catalyst.

  本发明涉及一种磷酸盐硼化合物，其由式(I)表示（以下简称化合物(I)）。本发明的目的是提供（A）一种新的工艺，通过简单的反应操作和高产率安全地在工业规模下生产化合物；（B）一种易于处理的新化合物；以及（C）新的用途作为催化剂。式(I)：（R1）（R2）（R3）PH.BAr4（I），其中R1，R2，R3和Ar如规范中所定义。工艺（A）包括将磷化物与a）HCl或b）H2SO4反应，以产生a）盐酸盐或b）硫酸盐；然后将盐与四芳基硼酸盐化合物反应。化合物（B）例如具有二级或三级烷基作为R1，在空气中易于处理而不需要特殊注意。用途（C）的特点是，化合物（I）代替过渡金属复合催化剂的不稳定磷化物化合物，用于催化C-C键，C-N键和C-O键形成反应，并且该化合物产生与过渡金属复合催化剂相同的效果。
• Process for producing phosphonium borate compound, novel phosphonium borate compound, and method of using the same
  申请人：Masaoka Shin

  公开号：US20090305877A1

  公开（公告）日：2009-12-10

  The invention relates to a phosphonium borate compound represented by Formula (I) (hereinafter, the compound (I)). The invention has objects of providing (A) a novel process whereby the compound is produced safely on an industrial scale, by simple reaction operations and in a high yield; (B) a novel compound that is easily handled; and (C) novel use as catalyst. Formula (I): (R 1 )(R 2 )(R 3 )PH.BAr 4 (I) wherein R 1 , R 2 , R 3 and Ar are as defined in the specification. The process (A) includes reacting a phosphine with a) HCl or b) H 2 SO 4 to produce a) a hydrochloride or b) a sulfate; and reacting the salt with a tetraarylborate compound. The compound (B) has for example a secondary or tertiary alkyl group as R 1 and is easily handled in air without special attention. The use (C) is characterized in that the compound (I) is used instead of an unstable phosphine compound of a transition metal complex catalyst for catalyzing C—C bond, C—N bond and C—O bond forming reactions and the compound produces an effect that is equal to that achieved by the transition metal complex catalyst.

  本发明涉及一种磷酸铵硼酸盐化合物，其化学式表示为（I）（以下简称化合物（I））。本发明的目的是提供（A）一种新的工艺，能够通过简单的反应操作和高产率安全地在工业规模上生产化合物；（B）一种易于处理的新化合物；以及（C）作为催化剂的新用途。 化学式（I）：（R1）（R2）（R3）PH·BAr4（I） 其中，R1、R2、R3和Ar的定义如规范中所述。 工艺（A）包括将磷化物与a）HCl或b）H2SO4反应，以产生a）盐酸盐或b）硫酸盐；然后将盐与四芳基硼酸盐化合物反应。 化合物（B）例如具有R1为次级或三级烷基，可以在空气中轻松处理，无需特别注意。 用途（C）的特点是，化合物（I）用于催化C-C键、C-N键和C-O键形成反应，而不是不稳定的过渡金属配合物催化剂中的磷化物化合物，其产生的效果与过渡金属配合物催化剂相当。
• Process for Producing Phosphonium Borate Compound, Novel Phosphonium Borate Compound, and Method of Using the Same
  申请人：MASAOKA Shin

  公开号：US20110166389A1

  公开（公告）日：2011-07-07

  The invention relates to novel phosphonium borate compounds represented by the Formula: (R 1 )(R 2 )(R 3 )PH.BAr 4 , wherein R 1 , R 2 , R 3 and Ar 4 are as defined herein, and compositions including such phosphonium borate compounds in combination with a transition metal, transition metal salt, transition metal oxide or transition metal complex for use in carbon-carbon bond forming reactions, carbon-nitrogen bond forming reactions and carbon-oxygen bond forming reactions.

  本发明涉及一种新型的磷酸盐硼酸盐化合物，其化学式表示为：（R1）（R2）（R3）PH.BAr4，其中R1、R2、R3和Ar4如本文所定义，并包括这种磷酸盐硼酸盐化合物与过渡金属、过渡金属盐、过渡金属氧化物或过渡金属配合物的组合物，用于碳-碳键形成反应、碳-氮键形成反应和碳-氧键形成反应。
• An Acidity Scale for Phosphorus-Containing Compounds Including Metal Hydrides and Dihydrogen Complexes in THF:  Toward the Unification of Acidity Scales
  作者：Kamaluddin Abdur-Rashid、Tina P. Fong、Bronwyn Greaves、Dmitry G. Gusev、Justin G. Hinman、Shaun E. Landau、Alan J. Lough、Robert H. Morris

  DOI：10.1021/ja994428d

  日期：2000.9.1

  More than 70 equilibrium constants K between acids and bases, mainly phosphine derivatives, have been measured in tetrahydrofuran (THF) at 20 degrees C by H-1 and/or P-31 NMR. The acids were chosen or newly synthesized in order to cover the, wide pK(a)(THF) range of 5-41 versus the anchor compound [HPCy3]BPh4 at 9.7. These pK(alpha)(THF) values-are approximations to absolute, free ion pK(a)(THF) and are obtained by crudely correcting the observed K for 1:1 ion-pairing effects by use of the Fuoss equation. The acid/base compounds include 14 phosphonium/phosphine couples, 17 cationic hydride/neutral hydride couples, 9 neutral polyhydride/anionic hydride couples, 14 dihydrogen/hydride couples, and 4 other nitrogen- and phosphorus-based acids. The effects on pK(alpha) of the:counterions BAr'(-)(4) and BF4- vs BPh4- and [K(2,2,2-crypt)](+) versus [K(18-crown-6)](+) are found to be minor after correcting for differences in inter-ion distances in the ion-pairs involved. Correlations with nu(M-H) noted here for the first time suggest that destabilization of M-H bonding in the conjugate base hydride is an important contributor to hydride acidity, It appears that Re-H bonding in the anions [ReH6(PR3)(2)](-) is greatly weakened by small increases in the basicity of PR3, resulting in a large increase in the pK(alpha) of the conjugate acid ReH7(PR3)(2) Correlations with other scales allow an estimate of the pK(alpha)(THF) values of more than 1000 inorganic and organic acids, 20 carbonyl hydride complexes, 46 cationic hydrides complexes, and dihydrogen gas. Therefore, many new acid-base reactions can be predicted and known reactions explained. THF, with its low dielectric constant, disfavors the ionization of neutral acids KA over HB+, and therefore separate lines are found for pK(alpha)(THF)(HA) and pK(alpha)(THF)(HB+) when plotted against pK(a)(DMSO) or pK(a)(MeCN). The crystal structure of [Re(H)(2)(PMe3)(5)]BPh4 is reported.
• Effect of the Ligand and Metal on the pKa Values of the Dihydrogen Ligand in the Series of Complexes [M(H2)H(L)2]+, M = Fe, Ru, Os, Containing Isosteric Ditertiaryphosphine Ligands, L
  作者：E. Paul Cappellani、Samantha D. Drouin、Guochen Jia、Patricia A. Maltby、Robert H. Morris、Caroline T. Schweitzer

  DOI：10.1021/ja00087a024

  日期：1994.4

  The new dihydrogen complexes trans-[MH(H-2)L(2)]BF4, L = P(C6H4-4-R)(2)CH2CH2P(C6H4-4-R)(2), R = CF3, M = Fe, Ru, and Os, R = CH3, M = Fe, R = OMe, M = Ru, are prepared by reaction of the dihydride complexes MH(2)L(2) With HBF4. The H-H bond length of the spinning H-2 ligand does not change significantly as a function of R (from CF3 to CH3 when M = Fe and from CF3 to OCH3 for M = Ru) according to H-1 NMR T-1 and (1)J(HD) measurements while there is a lengthening for the Os complexes. The rate constants for H atom exchange (reflecting the ease of homolytic splitting of H-2) increase with the increasing donor ability of R for a given metal as do the pK(a) values (reflecting a decrease in ease of heterolytic splitting). The electrochemical properties of some complexes MH(Cl)L(2) and MH(2)L(2) are reported. As expected H-2 acidity decreases as the parent hydride becomes easier to oxidize with this change in R (same M). The trend in dihydrogen pK(a) values as a function of the metal, Fe < Os < Ru, is distinctively different to the trend in pK(a) values of the dihydride complexes M(H)(2)(CO)(4), Fe < Ru < Os, and [M(C5H5)(H)(2)(PPh(3))(2)](+), Ru < Os, The high H-H bond energy of the RU(2+) complexes trans-[RuH(H-2)L(2)]BF4 is probably the reason why they are less acidic than corresponding Os2+ complexes. A consideration of the pK(a) values correctly indicated that a RuH(2)L(2)/[RuH(H-2)L(2)](+) mixture would be more effective at H/D exchange between D-2 and HO(t)Bu than the dihydrogen complex alone.