English

• 1.   Introduction

  Metal mediated functionalization of white phosphorus to phosphorus-based chemicals has been a hot area in recent years.^[1~5] One major interest in this field is searching for different types of polyphosphorus ligands, which is of fundamental theoretical significance despite that sometimes the yield is low. Among various polyphosphorus ligands, the search of different types of P₆ ligands derived from P₄ has been exploring. Since Scherer et al reported the first triple-decker sandwich molybdenum complex bearing a cyclo-P₆ ligand,^[6] the P₆ ligands of structural diversity have received continuous attention in both experimental characterization and theoretical calculations.^{[7, 8]} In 1980s, Scherer et al. characterized a series of transition metal cyclo-P₆ complexes in which the cyclo-P₆ ligands could be viewed as cyclo-P₆^6-, cyclo-P₆^4-, cyclo-P₆^2- and cyclo-P₆, respectively (Scheme 1a).^[9~11] Then, a binuclear thulium complex bearing a bicyclic P₆^6- ligand via thulium-mediated P₄ reductive functionalization was obtained (Scheme 1b).^[12] Later, a binuclear niobium complex bearing ^cP₃-^cP₃; ligand was documented (Scheme 1c).^[13] Besides P₆ ligands derived from P₄, a 3d/4f complex having ^cP₃-^cP₃ ligand^[14] (Scheme 1c) and these complexes bearing linear P₆^6- or P₆^4- ligands^{[15, 16]} (Scheme 1d) could also be obtained by other methods. Although four types of P₆ ligands have been reported, the new type of bicyclo[3.1.0]-P₆^4- ligand is unexplored (Scheme 1e).

  Scheme 1

  

  Scheme 1.  Representative examples of P₆ ligands

  下载: 全尺寸图片 幻灯片

  Rare-earth metals mediated functionalization of P₄ is rare due to the mismatch of the soft-hard properties between phosphorus and rare-earth metals.^[17] Recently, we have reported the reaction of Ph, TMS-substituted lutetacyclopentadienes with P₄ which affords the corresponding lutetium cyclo-P₃ complexes and phospholyl lithium.^{[18, 19]} Then, to investigate the substituent effect of lutetacyclopentadienes, the reaction of Me, TMS-substituted lutetacyclopentadienes with P₄ was carried out. In this reaction, a trinuclear rare-earth metal complex [{(η⁵-C₅Me₅)LuCl}₃(THF)P₆][Li(THF)₄] was isolated which contains the bicyclo[3.1.0]-P₆ ligand mentioned above. It also represents the first P₆ complex directly derived from P₄ involved rare-earth metals.

  2.   Results and discussion

  Reaction of two equivalents of Me, TMS-substituted lutetacyclopentadiene (1) with P₄ was carried out in THF at room temperature (Scheme 2). After 3 h, the expected cyclo-P₃ lutetium complex (2) and the aggregated phospholyl lithium (3) were obtained.^{[19b, 9c]} Besides, the sandwich lutetium complex (4) was isolated as a new complex. Interestingly, an unexpected trinuclear rare-earth metal complex [{(η⁵-C₅Me₅)LuCl}₃(THF)P₆][Li(THF)₄] (5) having a bicyclo[3.1.0]-P₆^4- ligand was also observed in this reaction.

  Scheme 2

  

  Scheme 2.  Reaction of 1 and P₄

  下载: 全尺寸图片 幻灯片

  The structure of 4 was determined by X-ray diffraction analysis which reveals that 4 crystallizes in the P2₁/c space group. There are two independent molecules of 4 in a unit cell which have the similar structural features so that Figure 1 shows one of them. The lutetium is supported by a Cp* ligand, a phospholyl ligand and two chlorine atoms. The lithium bridges the two chlorine atoms and also coordinates to two THF molecules. Both the bond lengths and the bond angles are located in the normal range compared to the known examples.^[20] In this reaction, 4 was formed directly from P₄ while the previous methods always need an additional step to prepare the phospholyl lithium, sodium or potassium first.^[21]

  Figure 1

  

  Figure 1.  ORTEP drawing of 4

  Ellipsoids are set at 30% probability level. Hydrogen atoms are omitted for clarity. Selected bond lengths [Å] and angles [°]: Lu(1)—P(1) 2.8651 (18), Lu(1)—C(1) 2.704(6), Lu(1)—C(2) 2.734(6), Lu(1)—C(3) 2.728(6), Lu(1)—C(4) 2.695(6), P(1)—C(1) 1.771(7), P(1)—C(4) 1.742(6), C(1)—C(2) 1.418(9), C(2)—C(3) 1.412(9), C(3)—C(4) 1.423(9); C(1)—P(1)—C(4) 91.5(3), P(1)—C(1)—C(2) 111.0(5), C(1)—C(2)—C(3) 112.5(6), C(2)—C(3)—C(4) 113.2(6), P(1)—C(4)—C(3) 111.3(5).

  下载: 全尺寸图片 幻灯片

  The structure of 5 was determined by X-ray diffraction analysis (Figure 2). The analysis reveals that 5 crystallizes in the P-1 space group. 5 is a separated ion pair consisting of a negative charged [P₆Lu₃] moiety and a lithium counter cation. The [P₆Lu₃] moiety has a pseudo mirror plane along the P(1)—P(4)—Lu(3) plane. Each lutetium is supported by a Cp* ligand and every two lutetiums have a bridging chlorine atom. Lu(1) and Lu(2) coordinate to the P₆ ligand in a η³ mode while Lu(3) coordinates in a η¹ mode. All of the Lu—P bond lengths are in the normal range of those found in the known lutetium phosphine or phosphide compounds (2.785~2.977 and 2.782~2.947 Å, respectively).^[22] The lutetium-phosphide bond lengths [Lu(1)—P(3), 2.729(3) Å; Lu(2)—P(5), 2.721(3) Å] are significantly shorter than the lutetium-phosphine bond lengths [Lu(1)—P(1), 2.828(3) Å; Lu(1)—P(4), 2.883(4) Å; Lu(2)—P(1), 2.822(3) Å; Lu(2)—P(4), 2.879(3) Å]. The bicyclo[3.1.0]-P₆ ligand takes a boat-like conformation composing of an envelope shaped five-membered ring and a three-membered ring. The P(2)—P(3)—P(5)—P(6) plane has an acute dihedral angle with the P(1)— P(2)—P(6) plane as 106.488°, while it has an obtuse dihedral angle with the P(3)—P(4)—P(5) plane as 132.771°. All the P—P bond lengths are in the typical range of P—P single bond length.^[1] The P—P bonds of the three-membered ring [P(1)—P(2), 2.236(5) Å; P(1)—P(6), 2.236(5) Å] are slightly longer than those of the five-membered ring [P(2)—P(3), 2.188(4) Å; P(3)—P(4), 2.182(4) Å; P(4)—P(5), 2.179(4) Å; P(5)—P(6), 2.179(4) Å], since the three-membered ring has a larger ring strain. In addition, upon Lu(1) and Lu(2) capping the puckered bicyclo-[3.1.0]-P₆ moiety, a [P₆Lu₂] cage is formed which could be viewed as an analogue of the known Zintl-P₇ cage^[23] by replacement of one edge P atom by two Lu atoms.

  Figure 2

  

  Figure 2.  ORTEP drawing of 5 (a) and its [P₆Lu₃Cl₃] core (b)

  Ellipsoids are set at 30% probability level. Hydrogen atoms, lithium counter cation and its coordinating THF molecules are omitted for clarity. Cp* ligands and THF are also omitted in the structure of the [P₆Lu₃Cl₃] core. Selected bond lengths [Å] and angles [°]: Lu(1)—P(1) 2.828(3), Lu(1)—P(3) 2.729(3), Lu(1)—P(4) 2.883(4), Lu(2)—P(1) 2.822(3), Lu(2)—P(4), 2.753(4), Lu(2)—P(5) 2.721(3), Lu(3)—P(4) 2.753(4), P(1)—P(2) 2.236(5), P(1)—P(6) 2.236(5), P(2)—P(3) 2.188(4), P(2)—P(6) 2.205(5), P(3)—P(4) 2.182(4), P(4)—P(5) 2.179(4), P(5)—P(6) 2.179(4); P(2)—P(1)—P(6) 59.10(15), P(1)—P(2)—P(3) 112.44(17), P(1)—P(2)—P(6) 60.46(15), P(3)—P(2)—P(6) 107.58(17), P(2)—P(3)—P(4) 97.79(16), P(3)—P(4)—P(5) 107.82(18), P(4)—P(5)—P(6) 97.96(17), P(1)—P(6)—P(2) 60.45(15), P(1)—P(6)—P(5) 112.80(18), P(2)—P(6)—P(5) 107.59(18)

  下载: 全尺寸图片 幻灯片

  To the best of our knowledge, it is the first time that the bicyclo[3.1.0]-P₆ ligand is incorporated into metal complexes, despite the fact that two neutral polyphosphane compounds with this P₆ motif linked with four ^tBu or Cp^* substituents have been reported.^{[24, 25]} Complex 5 is also the first example that rare-earth metal fragments activate P₄ affording a P₆ ligand.

  The ³¹P{¹H} NMR spectrum of 5 shows four sets of peaks corresponding to the four types of phosphorus atoms. The P(1) atom shows a triplet of triplet locating at δ -188.18 with ¹J_PP and ²J_PP values at about 198 and 48 Hz, respectively. The P(2)/P(6) atoms show a triplet of doublet locating at δ 9.63 with ¹J_PP and ¹J_PP values at about 208 and 90 Hz, respectively. The P(3)/P(5) atoms show a multiplet locating between δ -76.43 and -74.46. The P(4) atom shows a pseudo triplet locating at δ -31.91 with ¹J_PP value at about 372 Hz.

  To better understand the bonding between the three lutetium metals and the bicyclo[3.1.0]-P₆ ligand as well as the charge distribution of the negative charged P₆ ligand, density functional theory (DFT) calculations were performed to check canonical molecular orbitals (CMOs, Figure 3). HOMO shows that the lone electron pair of P(4) has an interaction with the d orbitals of both Lu(1) and Lu(2) simultaneously, which could be viewed as a P(4) centered three-center two-electron bond. Analogously, HOMO-2 show another three-center two-electron bond among P(1), Lu(1) and Lu(2) centered at P(1). HOMO-1 shows the interaction between P(3)/P(5) and Lu(1)/Lu(2), while HOMO-7 shows the interaction between P(4) and Lu(3). According to the NBO analysis, all of the P—P bonds are formed by overlap of their corresponding p orbitals, and all of the Lu—P bonds are formed by overlap of the p orbitals of the phosphorus atoms and the d orbitals of the lutetium metals.

  Figure 3

  

  Figure 3.  Selected canonical molecular orbitals of 5

  下载: 全尺寸图片 幻灯片

  3.   Conclusions

  In summary, we have isolated a trinuclear rare-earth metal complex 5 containing a bicyclo[3.1.0]-P₆ ligand, which is an unreported type and represents the first example that rare-earth metal fragments activate P₄ affording a P₆ ligand. The bonding situations of this novel complex 5 were discussed based on X-ray diffraction analysis and DFT calculations.

  4.   Experimental section

  4.1   Instruments and reagents

  All operations were performed under an atmosphere of dry nitrogen in a Vigor (SG 1200/750TS-F) glovebox. Anhydrous THF, hexane and toluene were purified using an Mbraun SPS-800 Solvent Purification System and dried over fresh Na chips in the glovebox. THF-d₈ was purchased from Cambridge Isotope Laboratory (CIL), degassed, and vacuum transferred to 4 Å molecular sieves. Organometallic samples for NMR spectroscopic measurements were prepared in the glovebox using J. Young valve NMR tubes (Wilmad 528-JY). NMR spectra were recorded on a Bruker Avance 400 MHz and a Bruker Avance 500 MHz spectrometers. ¹H NMR chemical shifts were reported with reference to solvent resonances of THF-d₈ at δ 3.58. ³¹P{¹H} NMR chemical shifts were reported with respect to 85% H₃PO₄ (aq.) (δ 0.0) standard. 1 was prepared according to the literature procedure.^[26] Other reagents were commercially available and used without further purification. Caution! P₄ is light-sensitive and highly flammable upon exposure to air. It should be handled with care.^[3c]

  4.2   Generation of the crystals of 2~5

  P₄ (123.9 mg, 1.0 mmol) was added to a THF solution (20 mL) of 1 (1298.4 mg, 2.0 mmol) in one portion. The reaction mixture was stirred at room temperature for 3 h and 1 was consumed completely monitored by ¹H NMR. After removal of the solvent under reduced pressure, the reddish yellow solid was extracted by 6 mL of hexane. The extract was concentrated to 4 mL at room temperature by volatilization and then stored at -25 ℃ for three days affording 3 as colorless crystals along with few yellowish red crystals referred to 5. After crystallization, the remaining supernatant liquid of the extract mainly contains 2 monitored by ³¹P{¹H} NMR. The residue was dissolved in 5 mL of THF. Then hexane (about 20 mL) was added till the first precipitation appears and the solution was stored at -25 ℃ affording the crystals of 4 along with that of 3.

  4.3   Generating the NMR spectra of 5

  The in situ ¹H NMR and ³¹P NMR showed no signal of 5 due to its low yield. 5 crystalized as several red crystals from the large proportion of yellowish colorless crystals 3. By isolating the red crystals one by one under microscope, about 3 mg of 5 was obtained although impurities still remain concomitant. The ³¹P NMR experiment was conducted at room temperature for about 1 h (scan number 1600). The ³¹P{¹H} COSY NMR experiment was conducted at room temperature for about 1 d.

  4.4   Determination of the yields of 2~5

  The NMR yields of 2~4 (13%, 45% and 40%, respectively) could be determined by ¹H NMR with hexamethylbenzene as internal standard. 5 couldn't be detected by the in situ ¹H NMR or ³¹P NMR because the yield of 5 is very low as about 1% (ca. 3 mg 5 was isolated).

  (η⁵-C₅Me₅)Lu{Me₂(SiMe₃)₂Li(THF)₃C₄P₃}] (2): ¹H NMR (400 MHz, THF-d₈) δ: 0.34 (s, 18H, SiMe₃), 1.76~1.79 (m, 12H, β-CH₂, THF), 1.93 (s, 15H, C₅Me₅), 2.22 (s, 6H, Me), 3.60~3.63 (m, 12H, α-CH₂, THF); ³¹P NMR (162 MHz, THF-d₈) δ: -85.15 (t, 1P,¹J_PP＝211.9 Hz, PLi), -199.46 (t, 2P,¹J_PP＝211.9 Hz, PC).

  {η⁵-C₄PMe₂(SiMe₃)₂}(η⁵-C₅Me₅)Lu{Cl₂Li(THF)₂} (4): ¹H NMR (400 MHz, THF-d₈) δ: 0.25 (s, 18H, SiMe₃), 1.76~1.79 (m, 8H, β-CH₂, THF), 1.99 (s, 15H, C₅Me₅), 2.19 (s, 6H, Me), 3.60~3.63 (m, 8H, α-CH₂, THF); ³¹P NMR (162 MHz, THF-d₈) δ: 159.49 (s).

  [{(η⁵-C₅Me₅)LuCl}₃(THF)P₆][Li(THF)₄] (5): ¹H NMR (500 MHz, THF-d₈) δ: 1.76~1.79 (m, 16H, β-CH₂, THF), 1.90 (s, 45H, C₅Me₅), 3.61~3.63 (m, 16H, α-CH₂, THF); ³¹P NMR (202 MHz, THF-d₈) δ: 9.63 (td,¹J_PP＝ca. 208 Hz,¹J_PP＝ca. 90 Hz, 2P, LuPPPPLi), -31.91 (t,¹J_PP＝ca. 372 Hz, 1P, LuPPPPLi), -74.46~76.43 (m, 2P, LuPPPPLi), -188.18 (tt,¹J_PP＝ca. 198 Hz,²J_PP＝ca. 48 Hz, 1P, LuPPPPLi).

  4.5   X-ray crystallographic studies

  Single crystals of 4 and 5 suitable for X-ray analysis were grown as shown in experimental section. The crystals were wrapped in mineral oil and then were frozen at 180 or 100 K. Data collections were performed at 180 or 100 K on a SuperNova diffractometer using graphite-monoch-romated Mo Kα radiation (λ＝0.71073 Å). Using Olex2,^[27] the structure were solved with the ShelXS or Superflip structure solution program using Charge Flipping^[28] and refined with the ShelXL refinement package using Least Squares minimization. Refinement was performed on F² anisotropically for all of the non-hydrogen atoms by the full-matrix least-squares method. The hydrogen atoms were placed at the calculated positions and were included in the structure calculation without further refinement of their parameters. Crystallographic data (excluding structure factors) have been deposited with the Cambridge Crystallographic Data Centre with supplementary publication numbers: CCDC 1869142 (4), 1869143 (5). These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

  SupportingInformation X-ray data of 4 and 5, Computational details of 5, and NMR spectra of new products. The Supporting Information is available free of charge via the Internet at http://sioc-journal.cn/.

• 1. [1]

     (a) Cossairt, B. M.; Piro, N. A.; Cummins, C. C. Chem. Rev. 2010, 110, 4164.
     (b) Caporali, M.; Gonsalvi, L.; Rossin, A.; Peruzzini, M. Chem. Rev. 2010, 110, 4178.
     (c) Scheer, M.; Balázs, G.; Seitz, A. Chem. Rev. 2010, 110, 4236.
     (d) Khan, S.; Sen, S. S.; Roesky, H. W. Chem. Commun. 2012, 48, 2169.

  2. [2]

     (a) Martin, C. D.; Weinstein, C. M.; Moore, C. E.; Rheingold, A. L.; Bertrand, G. Chem. Commun. 2013, 49, 4486.
     (b) Borger, J. E.; Ehlers, A. W.; Lutz, M.; Slootweg, J. C.; Lammertsma, K. Angew. Chem., Int. Ed. 2014, 53, 12836.
     (c) Arrowsmith, M.; Hill, M. S.; Johnson, A. L.; Kociok-Köhn, G.; Mahon, M. F. Angew. Chem., Int. Ed. 2015, 54, 7882.

  3. [3]

     (a) Piro, N. A.; Figueroa, J. S.; McKellar, J. T.; Cummins, C. C. Science 2006, 313, 1276.
     (b) Camp, C.; Maron, L.; Bergman, R. G.; Arnold, J. J. Am. Chem. Soc. 2014, 136, 17652.
     (c) Pinter, B.; Smith, K. T.; Kamitani, M.; Zolnhofer, E. M.; Tran, B. L.; Fortier, S.; Pink, M.; Wu, G.; Manor, B. C.; Meyer, K.; Baik, M.-H.; Mindiola, D. J. J. Am. Chem. Soc. 2015, 137, 15247.

  4. [4]

     (a) Zarzycki, B.; Bickelhaupt, F. M.; Radius, U. Dalton Trans. 2013, 42, 7468.
     (b) Yao, S.; Lindenmaier, N.; Xiong, Y.; Inoue, S.; Szilvási, T.; Adelhardt, M.; Sutter, J.; Meyer, K.; Driess, M. Angew. Chem., Int. Ed. 2015, 54, 1250.
     (c) Spitzer, F.; Graß l, C.; Balázs, G.; Zolnhofer, E. M.; Meyer, K.; Scheer, M. Angew. Chem., Int. Ed. 2016, 55, 4340.
     (d) Pelties, S.; Maier, T.; Herrmann, D.; de Bruin, B.; Rebreyend, C.; Gärtner, S.; Shenderovich, I. G.; Wolf, R. Chem. Eur. J. 2017, 23, 6094.

  5. [5]

     Mathey, F. Angew. Chem., Int. Ed. 2003, 42, 1578. doi: 10.1002/anie.200200557

  6. [6]

     Scherer, O. J.; Sitzmann, H.; Wolmershäuser, G. Angew. Chem., Int. Ed. Engl. 1985, 24, 351. doi: 10.1002/anie.198503511

  7. [7]

     Fleischmann, M.; Heindl, C.; Seidl, M.; Balázs, G.; Virovets, A. V.; Peresypkina, E. V.; Tsunoda, M.; Gabbaï, F. P.; Scheer, M. Angew. Chem., Int. Ed. 2012, 51, 9918. doi: 10.1002/anie.201204686

  8. [8]

     (a) Warren, D. S.; Gimarc, B. M. J. Am. Chem. Soc. 1992, 114, 5378.
     (b) Hiberty, P. C.; Volatron, F. Heteroat. Chem. 2007, 18, 129.

  9. [9]

     Scherer, O. J.; Swarowsky, H.; Wolmershäuser, G.; Kaim, W.; Kohlmann, S. Angew. Chem., Int. Ed. Engl. 1987, 26, 1153. doi: 10.1002/anie.198711531

  10. [10]

      Scherer, O. J.; Schwalb, J.; Swarowsky, H.; Wolmershäuser, G.; Kaim, W.; Gross, R. Chem. Ber. 1988, 121, 443. doi: 10.1002/cber.19881210309

  11. [11]

      Scherer, O. J.; Vondung, J.; Wolmershäuser, G. Angew. Chem., Int. Ed. Engl. 1989, 28, 1355. doi: 10.1002/anie.198913551

  12. [12]

      Scherer, O. J.; Werner, B.; Heckmann, G.; Wolmershäuser, G. Angew. Chem., Int. Ed. Engl. 1991, 30, 553. doi: 10.1002/anie.199105531

  13. [13]

      Hulley, E. B.; Wolczanski, P. T.; Lobkovsky, E. B. Chem. Commun. 2009, 6412.

  14. [14]

      Arleth, N.; Gamer, M. T.; Köppe, R.; Pushkarevsky, N. A.; Konchenko, S. A.; Fleischmann, M.; Bodensteiner, M.; Scheer, M.; Roesky, P. W. Chem. Sci. 2015, 6, 7179. doi: 10.1039/C5SC02252E

  15. [15]

      Vaira, M. D.; Stoppioni, P. Polyhedron 1994, 13, 3045. doi: 10.1016/S0277-5387(00)83669-4

  16. [16]

      Wiśniewska, A.; Łapczuk-Krygier, A.; Baranowska, K.; Chojnacki, J.; Matern, E.; Pikies, J.; Grubba, R. Polyhedron 2013, 55, 45. doi: 10.1016/j.poly.2013.02.046

  17. [17]

      (a) Konchenko, S. N.; Pushkarevsky, N. A.; Gamer, M. T.; Köppe, R.; Schnöckel, H.; Roesky, P. W. J. Am. Chem. Soc. 2009, 131, 5740.
      (b) Huang, W.; Diaconescu, P. L. Chem. Commun. 2012, 48, 2216.
      (c) Huang, W.; Diaconescu, P. L. Eur. J. Inorg. Chem. 2013, 4090.
      (d) Selikhov, A. N.; Mahrova, T. V.; Cherkasov, A. V.; Fukin, G. K.; Kirillov, E.; Lamsfus, C. A.; Maron, L.; Trifonov, A. A. Organometallics 2016, 35, 2401.
      (e) Schoo, C.; Bestgen, S.; Köppe, R.; Konchenko, S. N.; Roesky, P. W. Chem. Commun. 2018, 54, 4770.

  18. [18]

      Ma, W.; Yu, C.; Chen, T.; Xu, L.; Zhang, W.-X.; Xi, Z. Chem. Soc. Rev. 2017, 46, 1160. doi: 10.1039/C6CS00525J

  19. [19]

      (a) Xu, L.; Chi, Y.; Du, S.; Zhang, W.-X.; Xi, Z. Angew. Chem., Int. Ed. 2016, 55, 9187.
      (b) Du, S.; Yin, J.; Chi, Y.; Xu, L.; Zhang, W.-X. Angew. Chem., Int. Ed. 2017, 56, 15886.
      (c) Du, S.; Zhang, W.-X.; Xi, Z. Organometallics 2018, 37, 2018.
      (d) Du, S.; Hu, J.; Chai, Z.; Zhang, W.-X.; Xi, Z. Chin. J. Chem. 2019, 37, 71.

  20. [20]

      (a) Nief, F.; Mathey, F. J. Chem. Soc., Chem. Commun. 1989, 800.
      (b) Fontaine, F.-G.; Tupper, K. A.; Tilley, T. D. J. Organomet. Chem. 2006, 691, 4595.

  21. [21]

      (a) Jaroschik, F.; Shima, T.; Li, X.; Mori, K.; Ricard, L.; Le Goff, X.-F.; Nief, F.; Hou, Z. Organometallics 2007, 26, 5654.
      (b) Xu, Y.; Wang, Z.; Gan, Z.; Xi, Q.; Duan, Z.; Mathey, F. Org. Lett. 2015, 17, 1732.

  22. [22]

      (a) Zhang, L.; Suzuki, T.; Luo, Y.; Nishiura, M.; Hou, Z. Angew. Chem., Int. Ed. 2007, 46, 1909.
      (b) Masuda, J. D.; Jantunen, K. C.; Ozerov, O. V.; Noonan, K. J. T.; Gates, D. P.; Scott, B. L.; Kiplinger, J. L. J. Am. Chem. Soc. 2008, 130, 2408.

  23. [23]

      (a) Turbervill, R. S. P.; Goicoechea, J. M. Chem. Rev. 2014, 114, 10807; (b) Hennersdorf, F.; Frötschel, J.; Weigand, J. J. J. Am. Chem. Soc. 2017, 139, 14592.

  24. [24]

      Baudler, M.; Aktalay, Y.; Tebbe, K. F.; Heinlein, T. Angew. Chem., Int. Ed. Engl. 1981, 20, 967. doi: 10.1007/978-3-322-85352-3_1

  25. [25]

      Jutzi, P.; Kroos, R.; Möller, A.; Bögger, H.; Penk, M. Chem. Ber. 1991, 124, 75. doi: 10.1002/cber.19911240112

  26. [26]

      (a) Xu, L.; Wang, Y.-C.; Wei, J.; Wang, Y.; Wang, Z.; Zhang, W.-X.; Xi, Z. Chem. Eur. J. 2015, 21, 6686.
      (b) Xu, L.; Wei, J.; Zhang, W.-X.; Xi, Z. Chem. Eur. J. 2015, 21, 15860.
      (c) Xu, L.; Wang, Y.; Wang, Y.-C.; Wang, Z.; Zhang, W.-X.; Xi, Z. Organometallics 2016, 35, 5.

  27. [27]

      Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. J. Appl. Cryst. 2009, 42, 339. doi: 10.1107/S0021889808042726

  28. [28]

      Palatinus, L.; Chapuis, G. J. Appl. Cryst. 2007, 40, 786. doi: 10.1107/S0021889807029238

• 

  Scheme 1  Representative examples of P₆ ligands

  下载: 全尺寸图片 幻灯片
  

  Scheme 2  Reaction of 1 and P₄

  下载: 全尺寸图片 幻灯片
  

  Figure 1  ORTEP drawing of 4

  Ellipsoids are set at 30% probability level. Hydrogen atoms are omitted for clarity. Selected bond lengths [Å] and angles [°]: Lu(1)—P(1) 2.8651 (18), Lu(1)—C(1) 2.704(6), Lu(1)—C(2) 2.734(6), Lu(1)—C(3) 2.728(6), Lu(1)—C(4) 2.695(6), P(1)—C(1) 1.771(7), P(1)—C(4) 1.742(6), C(1)—C(2) 1.418(9), C(2)—C(3) 1.412(9), C(3)—C(4) 1.423(9); C(1)—P(1)—C(4) 91.5(3), P(1)—C(1)—C(2) 111.0(5), C(1)—C(2)—C(3) 112.5(6), C(2)—C(3)—C(4) 113.2(6), P(1)—C(4)—C(3) 111.3(5).

  下载: 全尺寸图片 幻灯片
  

  Figure 2  ORTEP drawing of 5 (a) and its [P₆Lu₃Cl₃] core (b)

  Ellipsoids are set at 30% probability level. Hydrogen atoms, lithium counter cation and its coordinating THF molecules are omitted for clarity. Cp* ligands and THF are also omitted in the structure of the [P₆Lu₃Cl₃] core. Selected bond lengths [Å] and angles [°]: Lu(1)—P(1) 2.828(3), Lu(1)—P(3) 2.729(3), Lu(1)—P(4) 2.883(4), Lu(2)—P(1) 2.822(3), Lu(2)—P(4), 2.753(4), Lu(2)—P(5) 2.721(3), Lu(3)—P(4) 2.753(4), P(1)—P(2) 2.236(5), P(1)—P(6) 2.236(5), P(2)—P(3) 2.188(4), P(2)—P(6) 2.205(5), P(3)—P(4) 2.182(4), P(4)—P(5) 2.179(4), P(5)—P(6) 2.179(4); P(2)—P(1)—P(6) 59.10(15), P(1)—P(2)—P(3) 112.44(17), P(1)—P(2)—P(6) 60.46(15), P(3)—P(2)—P(6) 107.58(17), P(2)—P(3)—P(4) 97.79(16), P(3)—P(4)—P(5) 107.82(18), P(4)—P(5)—P(6) 97.96(17), P(1)—P(6)—P(2) 60.45(15), P(1)—P(6)—P(5) 112.80(18), P(2)—P(6)—P(5) 107.59(18)

  下载: 全尺寸图片 幻灯片
  

  Figure 3  Selected canonical molecular orbitals of 5

  下载: 全尺寸图片 幻灯片
•