(diphenylphosphinoamino)diphenylphosphine oxide | 7648-76-2

• 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: (diphenylphosphinoamino)diphenylphosphine oxide
• 英文别名: Tetraphenyl-iminodiphosphinoxide；[(diphenylphosphorylamino)-phenylphosphanyl]benzene
• CAS: 7648-76-2
• 化学式: C₂₄H₂₁NOP₂
• 分子量: 401.384
• InChiKey: XXLMYCOFZHFKQO-UHFFFAOYSA-N

物化性质

• 沸点：
  541.9±33.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (diphenylphosphinoamino)diphenylphosphine oxide 在 t-BuOK 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 生成 cis-[Pt(Ph2PNP(O)Ph2-P,O)2]
  参考文献：
  名称：

  Palladium(II) and Platinum(II) Complexes of the Heterodifunctional Ligand Ph₂PNHP(O)Ph₂

  摘要：

  The noncomplexed ligand Ph(2)PNHP(O)Ph(2) (HL) has been prepared, for the first time, from Ph(2)PNHPPh(2) (dppa) and H2O2 in moderate yield. On further treatment with H2O2 the phosphine oxide Ph(2)P(O)NHP(O)Ph(2) (1) can be formed. Reaction of [MCl(2)(COD)] (M = Pt or Pd; COD = cycloocta-1,5-diene) with 2 molar equiv of HL affords [MCl(2)(HL)(2)] (4, 5) in which both ligands are monodentate P-bound. The analogous dibromo and diiodo derivatives [MX(2)(HL)(2)] (6-9) were prepared from either [MX(2)(COD)] (M = Pt or Pd; X = Br or I) and HL or treatment of [MCl(2)(HL)(2)] with an excess of NaI. Facile base deprotonation of the amine proton in 4 or 5 affords a new class of metallacycles [M(L)(2)] [L(-) = Ph(2)PNP(O)Ph(2)(-)] (10, 11) incorporating two five-membered M-P-N-P-O rings. Compound 10 was independently made from [Pt(CH3)(2)(COD)] and 2 equiv of HL in toluene at ambient temperature whereas the reaction of [Pt(CH3)Cl(COD)] with 2 equiv of HL affords solely trans-[Pt(CH3)Cl(HL)(2)] (13). Protonation of the neutral compound 10 with HCl in ethanol regenerates the ring-opened cis complex 4. In contrast, addition of HBF4 . OEt(2) to 10 (or 11) results in exclusive protonation at the nitrogen atom of the chelating ligands to give cis-[M{Ph(2)PNHP(O)Ph(2)-P,O}(2)][BF4](2) (15, 16); both chelate rings remain intact. The dicationic compounds 15, 16 can also be synthesized from 4, 5 in dichloromethane using Ag[BF4] as a chloride abstractor. All new compounds described have been characterized by a combination of multinuclear NMR spectroscopy, IR spectroscopy, and elemental analyses. The molecular structures of Ph(2)PNHP(O)Ph(2), cis-[PtBr2{Ph(2)PNHP(O)Ph(2)-P}(2)], cis-[Pt{Ph(2)PNP(O)Ph(2)-P, O}(2)], trans-[Pt(CH3)Cl{Ph(2)PNHP(O)Ph(2)-P}(2)] and cis-[Pt{Ph(2)PNHP(O)Ph(2)-P, O}(2)][BF4](2) have been determined by single-crystal X-ray diffraction. Crystals of HL are triclinic, space group P (1) over bar, with a = 10.410(2) Angstrom, b = 12.083(2) Angstrom, c = 9.036(4) Angstrom, alpha = 103.05(2)degrees, beta = 99.09(2)degrees, gamma = 72.98(1)degrees, V = 1054 Angstrom(3), and Z = 2. The final R and R(w) values were 0.061 and 0.047, respectively. Crystals of 6 are triclinic, space group P (1) over bar, with a = 13.113(4) Angstrom, b = 15.996(4) Angstrom, c = 13.011(4) Angstrom, alpha = 102.65(3)degrees, beta = 117.39(2)degrees, gamma = 101.03(2)degrees, V = 2225 Angstrom(3), and Z = 2. The final R and R(w) values were 0.039 and 0.031, respectively. Crystals of 10 are monoclinic, space group P2(1)/a, with a 17.600(13) Angstrom, b = 13.498(10) Angstrom, c = 18.641(9) Angstrom, beta = 105.13(1)degrees, V = 4274 Angstrom(3), and Z = 4. The final R and R(w) values were 0.041 and 0.036, respectively. Crystals of 13 are triclinic, space group P (1) over bar, with a = 14.686(2) Angstrom, b = 18.735(2) Angstrom, c = 9.018(3) Angstrom, alpha = 91.71(2)degrees, beta = 102.27(2)degrees, gamma = 68.54(1)degrees, V = 2253 Angstrom(3), and Z = 2. The final R and R(w) values were 0.041 and 0.044, respectively. Crystals of 15 are orthorhombic, space group P2(1)2(1)2, with a = 14.100(2) Angstrom, b = 19.002(1) Angstrom, c = 9.145(2) Angstrom, V = 2450 Angstrom(3), and Z = 2. The final R and R(w) values were 0.052 and 0.057, respectively. The P-bound monodentate complexes contain ligands with similar bond lengths to the neutral compound, while deprotonation/chelation results in lengthening of the P-O and shortening of the P-N bond length as a result of electronic delocalization.

  DOI：

  10.1021/ic951247d
• 作为产物：
  描述：

  N,N-双(二苯磷)胺 在 双氧水 作用下， 生成 (diphenylphosphinoamino)diphenylphosphine oxide
  参考文献：
  名称：

  P–N–S/Se-containing metallacycles

  摘要：

  Metal complexes containing only Group 15 and 16 elements in the chelate rings are studied extensively in M-S-N chemistry. Recently M-E-P-N type systems are starting to reveal interesting conformational and structural properties;. examples of syntheses and structures are provided. The cover shows the crystal structures (DIAMOND drawings) of [M{(Pr2P)-P-1(S)NP(S)Pr-2(1)}(2)] (M = Pd or Pt) illustrating the surprising conformational change effected by replacing a palladium by a platinum centre.

  DOI：

  10.1039/dt9960002893

文献信息

• Synthesis and characterisation of E,O-mixed donor (E=P, S or Se) ligand complexes of palladium(II) and platinum(II)
  作者：Martin B Smith*、Alexandra M.Z Slawin*

  DOI：10.1016/s0020-1693(99)00493-4

  日期：2000.3

  [Pd(μ-Cl)(C 12 H 9 N 2 )} 2 ] with the unsymmetrical anions [Ph 2 P(E)NP(O)Ph 2 ] − (E=S or Se) gave the square–planar complexes [Pd(C 12 H 9 N 2 )Ph 2 P(E)NP(O)Ph 2 - E , O }] exclusively as one isomer (E trans to N). In a similar manner the new metal(II) compounds [PtClPh 2 P(E)NP(O)Ph 2 - E , O }(PMe 2 Ph)] (E trans to Cl) and [Pd(C 9 H 15 O)Ph 2 P(E)NP(O)Ph 2 - E , O }] (E trans to olefin double bond)

  摘要具有杂配体Ph 2 PNHP（O）Ph 2，[Ph 2 PNP（O）Ph 2]-或[Ph 2 P（E）NP（O）Ph 2的新型钯（II）和铂（II）配合物]-（E = S或Se）已经准备好并进行了表征。因此，环金属化二聚体[Pd（μ-Cl）（C〜N）} 2] [C〜N = C 12 H 9 N 2或C 13 H 8 N]与Ph 2 PNHP（O）Ph 2的反应得到单核化合物[PdCl（C〜N）Ph 2 PNHP（O）Ph 2-P}]。氯化物提取或胺去质子化得到[Pd（C〜N）Ph 2 PNHP（O）Ph 2-P，O}] [BF 4]或[Pd（C〜N）Ph 2 PNP（O）Ph 2-P，O}]分别带有中性或阴离子P，O螯合配体。[Pd（μ-Cl）（C 9 H 12 N）} 2与Ph 2 PNHP（O）Ph 2在CDCl 3溶液中的反应产生了已知的，相当不稳定的化合物[PdCl（C
• Osmacycles containing the {(Ph2PE)2N}− ligand (E=S or Se): synthesis and crystal structures
  作者：Jonathan Parr、Martin B Smith、Mark R.J Elsegood

  DOI：10.1016/s0022-328x(02)01967-8

  日期：2002.12

  (dppa) or Ph2PN(H)P(O)Ph2 (HL) with [Os(η6-cym)Cl2]2 [cym=p-CH3C6H4CH(CH3)2] in THF affords the orange, neutral mononuclear complexes [OsCl2(η6-cym)P-dppa] (1a) or [OsCl2(η6-cym)P-HL] (2), respectively, bearing a pendant PPh2 or P(O)Ph2 group. Complex 1a isomerises smoothly in CDCl3 solution to give the cationic P,P′-chelate complex [OsCl(η6-cym)P,P′-dppa]Cl (1b). Compound 2 can further be converted

  的反应（PH 2 P）2 NH（DPPA）或PH 2 PN（H）P（O）PH 2（HL）以[OS（η 6 -cym）氯2 ] 2 [CYM = p -CH 3 Ç 6 ħ 4 CH（CH 3）2 ]在THF，得到橙色，中性单核配合物[OSCL 2（η 6 -cym）P -dppa]（1A）或[OSCL 2（η 6 -cym）P -HL]（2）分别带有侧PPh 2或P（O）PH2组。复杂1A顺利isomerises在CDCl 3溶液，得到阳离子P，P ' -螯合物配合物[OSCL（η 6 -cym）P，P ' -dppa]氯（1B）。化合物2可进一步被转化为黄色P，ö螯合物配合物[OSCL（η 6 -cym）P，ö -HL] [BF 4 ]（3）和[OSCL（η 6 -cym）P，Ô -L ]（4）[L = Ph 2 PNP（O）Ph2 ]分别用Ag [BF 4 ]或t BuOK处理。[OS（η的氯桥裂解6
• Late transition-metal complexes with the heterofunctional phosphine Ph2PNHP(O)Ph2
  作者：Alexandra M. Z. Slawin、Martin B. Smith、J. Derek Woollins

  DOI：10.1039/dt9960001283

  日期：——

  Removal of the amine proton in metal complexes of HL (monodenate P-bound) with KOBut afforded a new class of neutral metallacycles incorporating either an MP2NO or M2P4N2O2 framework based on the [Ph2PNP(O)Ph2]–(L–) ligand. Reaction of [Pd(µ-Cl)-(C9H12N)}2] with 4 equivalents of HL in methanol at ambient temperature yielded the neutral palladium(II) complex [PdClPh2PNP(O)Ph2-P,O}(Ph2POMe)] in which

  的配合物[的MC1（COD）（HL）]（M =铑或铱），[的PdCl（η 3 -C 3 H ^ 5）（HL）]，[的PdCl（L-L）（HL）]，反式- [ RhCl（CO）（HL）2 ]和[AuCl（HL）]是通过[M（µ-Cl）（cod）} 2 ]（M = Rh或Ir; cod =环辛1-1， 5二烯），[的Pd（μ-Cl）的（η 3 -C 3 H ^ 5）} 2 ]，[的Pd（μ-Cl）的（L-L）} 2 ]（L-L = C 12 ħ 12 N，C 10 H 8 N或C 9 H 12 N），[Rh（µ-Cl）（CO）2 } 2]或[AuCl（tht）]（tht =四氢噻吩）与Ph 2 PNHP（O）Ph 2（HL）。在所有这些络合物中，配体都是单价的P结合的。从氯化物抽象[的PdCl（C 12 H ^ 12 N）（HL）]或[的PdCl（η 3 -C 3 H ^ 5）（HL）]时，使用的Ag
• Synthesis and catalytic activity of allyl, methallyl and methyl complexes of nickel(II) and palladium(II) with biphosphine monoxide ligands: oligomerization of ethylene and copolymerization of ethylene and carbon monoxide
  作者：Ingo Brassat、Wilhelm Keim、Stefan Killat、Melanie Möthrath、Piero Mastrorilli、Cosimo Francesco Nobile、Gian Paolo Suranna

  DOI：10.1016/s1381-1169(99)00449-5

  日期：2000.6

  The syntheses of new cationic nickel complexes [eta(3)-methallyl]Ni[ kappa (2) P,O-Ph(2) P(X)P(O)Ph(2)]}SbF(6), (1)-(2) [X = (o-C(6)H(4)) (1), (NH), (2)1 have been accomplished. The complexes oligomerize ethylene to linear cl-olefins with selectivities as high as 89%. A dependence of oligomerization grade and activity on backbone geometry was shown. New cationic allyl and methyl complexes of palladium(II) [(CH(3)CN)(Me)Pd(kappa(2)P,O-Ar(2)P(CH(2))(n)P(O)Ar(2))]X [n = 1-3, X = BF(4), Ar = C(6)H(5) (18-20)] [n = 1, X = SbF(6), Ar =p-tolyl (23); n = 1 or 2, X = SbF(6), Ar = C(6)H(5) (21) or (22)]; [( eta(3)-C(3)H(5)Pd(kappa(2)P,O- Ph(2)P(CH(2))(n)P(O)Ph(2))]X, [n = 2, X=triflate (10), tosylate (13); n=3, X=triflate (11), tosylate (14)], ([ eta(3)- C(3)H(5))]Pd(kappa(2)P,O-Ar(2)P(CH(2))(n)P(O)Ar(2))]X, [n = 1, X = SbF(6), Ar =p-tolyl (17); n = 2, X = SbF(6) Ar = C(6)H(5)(16)] have been synthesized in good yields. These complexes have been used in the catalytic oligomerization of ethylene, and in the catalytic alternating copolymerization of ethylene and carbon monoxide, to yield polyketones. (C) 2000 Elsevier Science B.V. All rights reserved.
• New hydrogen-bonded dimeric and polymeric gold(I) complexes of the heterodifunctional ligand Ph2PNHP(O)Ph2
  作者：Alexandra M.Z Slawin、Martin B Smith、J.Derek Woollins

  DOI：10.1016/s0277-5387(98)00405-7

  日期：1999.3

  The preparation of several new gold(I) complexes by chloride metathesis of [AuCl(HL)] [HL=Ph2PNHP(O)Ph-2] with either HL or K[Ph2P(E)NP(E)Ph-2] (E=S or Se) is described. All compounds were characterised by a combination of P-31H-1}, H-1 and IR spectroscopy, microanalysis and X-ray crystallography. X-ray structural studies reveal that [Au(HL)(2)]Cl [monoclinic, space group P2(1)/c, a=9.0726(3) Angstrom, b=21.0847(6) Angstrom, c=12.0131(3) Angstrom, beta=105.1090(10)degrees, V=2219 Angstrom(3), Z=2, final R=3.97] forms a one dimensional polymeric structure in which alternating [Au(HL)(2)](+) and Cl- ions are linked through intermolecular N-K ... Cl hydrogen-bonding. In contrast the three-co-ordinate compound [AuPh2P(Se)NP(Se)Ph-2-Se,Se'}(HL)] [monoclinic, space group P2(1)/a, a=21.6752(5) Angstrom, b=9.1200(10) Angstrom, c=24.0742(7) Angstrom, beta=106.080(2)degrees, V=4573 Angstrom(3), Z=4, final R=8.94] forms hydrogen-bonded dimer pairs analogous to that previously observed in non-complexed HL. The X-ray crystal structure of the gold(I) precursor [AuCl(HL)] has also been determined: monoclinic, space group P2(1)/c, a=10.217(8) Angstrom, b =23.256(5) Angstrom, c=20.086(5) Angstrom, beta = 101.15(4)degrees, V=4683 Angstrom(3), Z=8, final R=5.2. The X-ray crystal structure reveals intermolecular N-H ... O=P hydrogen-bonding between adjacent [AuCl(HL)] molecules forming infinite chains. (C) 1999 Elsevier Science Ltd. All rights reserved.