[(CrGe9)Cr2(CO)13]4-: A disubstituted case of ten-vertex closo cluster with spherical aromaticity

Citation: Ya-Shan Huang, Dandan Chen, Jun Zhu, Zhong-Ming Sun. [(CrGe₉)Cr₂(CO)₁₃]^4-: A disubstituted case of ten-vertex closo cluster with spherical aromaticity[J]. Chinese Chemical Letters, 2022, 33(4): 2139-2142. doi: 10.1016/j.cclet.2021.08.038 shu

[(CrGe₉)Cr₂(CO)₁₃]^4-: A disubstituted case of ten-vertex closo cluster with spherical aromaticity

English

[(CrGe₉)Cr₂(CO)₁₃]^4-: A disubstituted case of ten-vertex closo cluster with spherical aromaticity

a.
State Key Laboratory of Elemento-Organic Chemistry, Tianjin Key Lab of Rare Earth Materials and Applications, School of Material Science and Engineering, Nankai University, Tianjin 300350, China
b.
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
^* Corresponding authors.
E-mail address: sunlab@nankai.edu.cn (Z.-M. Sun).
Received Date: 15 July 2021
Accepted Date: 09 August 2021
Revised Date: 06 August 2021
Available Online: 15 April 2022

Abstract: We report the first disubstituted hetero-ten-vertex closo cluster [(CrGe₉)Cr₂(CO)₁₃]^4- with three adjacent Cr(CO)_n units adopting both η⁵ and η¹ coordination modes, which was synthesized through the reaction of "KGe_1.67" with (MeCN)₃Cr(CO)₃ and Cr(CO)₆ in ethylenediamine (en) solution. In contrast to the η¹-Cr atoms forming localized two-center two-elelctron (2c-2e) Cr-Ge bonds, the hetero atom η⁵-Cr exhibits versatile bonding mechanisms including three 5c-2e and five 8c-2e delocalized bonds which account for Hückel aromaticity. Intricate multi-center bonding patterns delineate the multiple local σ-aromatic characters of the title cluster displaying explicit spherical aromaticity.

Key words:

The chemistry of Group 14 zintl ions covers extensive studies of nine-atom deltahedral clusters, whereas those of ten-atom closo clusters remain relatively limited [1-10]. Albeit two homoatomic clusters E₁₀^2- (E = Ge, Pb) have been isolated from solution reactions [11, 12], most of the structurally characterized ten-atom clusters are doped with at least one metal atom. At variance with most heteroatomic clusters capped by transition-metal fragments, such as [(η⁴-E₉)M(CO)₃]^4- (E = Sn, Pb; M = Cr, Mo, W) [13, 14], [E₉Zn-Ph]^3- (E = Si, Ge, Sn, Pb) [15], [NHC^DippMSn₉]^3- (M = Cu, Ag, Au) [16], [E₉Cd(C₆H₅)]^3- (E = Sn, Pb) [17] and [Ge₉Ni-CO]^3- [18], alternative coordination modes have been observed, for example, one Mo(CO)₃ fragment in the [(η⁵-Pb₉)Mo(CO)₃]^4- occupying a waist vertex [19]. Recently, another ten-vertex cluster [Ge₈(Mo(CO)₃)₂]^4- with two waist vertices replaced by Mo(CO)₃ fragments has also been reported [20]. The inherent stability of closo architecture imparts to elusive substitution on such type of clusters. Not much has been known about the functionalized clusters, since only one monosubstituted ten-vertex cluster [Ge₁₀Mn(CO)₄]^3- was isolated [21]. Herein, we report the isolation of a disubstituted hetero ten-vertex closo cluster derivative [K(2.2.2-crypt)]₄[(CrGe₉)Cr₂(CO)₁₃]·tol (1). Structural characterization and calculations revealed an unusual arrangement of three adjacent Cr(CO)_n fragments, wherein both η⁵ and η¹ coordination modes jointly interpret the sophisticated bonding pattern which further leads to multiple local aromaticity in the title cluster.

The title cluster [(CrGe₉)Cr₂(CO)₁₃]^4- (1a, Fig. 1) was obtained from the reaction of "KGe_1.67" with (MeCN)₃Cr(CO)₃ and Cr(CO)₆ in en in the presence of 2.2.2-crypt. Single-crystal X-ray diffraction reveals that the complex crystallizes in the triclinic space group P1 and the asymmetric unit contains one crystallographically distinct 1a with four [K(2.2.2-crypt)]⁺ cations as well as one solvent molecule of toluene, and an interaction was observed between one carbonyl group of 1a and [K(2.2.2-crypt)]⁺ (Fig. S2 in Supporting information).

Figure 1

Figure 1. Structure of [(CrGe₉)Cr₂(CO)₁₃]^4- (1a) (thermal ellipsoids of heavy atoms drawn at 50% probability). DFT-optimized bond distances are available in Supporting information.

DownLoad: Full-Size Img PowerPoint

Strong signals of the parent anions {H[K(2.2.2-crypt)]₂[Ge₉Cr₃ (CO)₁₃]}^- and {H₂[K(2.2.2-crypt)][Ge₉Cr₃(CO)₁₃]}^- (Fig. 2 and Fig. S6 in Supporting information) were observed in the electrospray ionization mass spectra (ESI-MS) of 1 in DMF. In addition, the ESI-MS revealed a signal of {H₂[K(2.2.2-crypt)][Ge₉Cr₂(CO)₈]}^- (Fig. S5 in Supporting information) ion losing one Cr(CO)₅ fragment. The successful isolation of the [(η⁵-Pb₉)Mo(CO)₃]^4- reminded us the possible existence of [(η⁵-Ge₉)Cr(CO)₃]^4-. However, all attempts to obtain [Ge₉Cr₂(CO)₈]^4- and [(η⁵-Ge₉)Cr(CO)₃]^4- by changing the precursor and reaction conditions proved unsuccessful.

Figure 2

Figure 2. Negative ion mode ESI mass peak corresponding to {H[K(2.2.2-crypt)]₂[Ge₉Cr₃(CO)₁₃]}^-. The recorded experimental data is shown in black with the calculated isotopic distributions in red.

DownLoad: Full-Size Img PowerPoint

The structure of [(CrGe₉)Cr₂(CO)₁₃]^4- is best described as a hetero-ten-atom closo cluster [CrGe₉] with a waist vertex occupied by the Cr(CO)₃ and two coordinated Cr(CO)₅ fragments on the positions of Ge2 and Ge9 in η¹: η¹-coordination modes. Not only the shape of [CrGe₉] defines it as a closo cluster but its charge and electron count. The anionic cluster 1a with a total of 22 skeleton electrons, provided by 9 Ge-atoms (2 electrons each) and one Cr(CO)₃ fragment (0 electron) as well as the charge (4 additional electrons), is in accordance with the Wade-Mingos rules for a ten-atom closo cluster [22, 23].

Insertion of the Cr(CO)₃ fragment results in the distorted ten-vertex cage with a compressed Ge₄ square (2.6659(11)-2.8670(11) Å) and an extended CrGe₃ square (2.8104(12)-3.0324(12) Å). The Ge-Ge distances range from 2.5073(11) Å to 2.8670(11) Å and are comparable to those observed in other germanium clusters [24-31]. The very long Cr-Ge bond distances (Cr1-Ge6/Cr1-Ge7: 2.8814(13) Å /2.9061(14) Å) are located in the extended CrGe₃-square, while the shortest (Cr1-Ge9: 2.5199(14) Å) is the bond between the Cr-vertex and the Ge-atom exo-bonded to Cr(CO)₅, only 0.02-0.06 Å shorter than other distances at the exo-bonded germanium atoms (Cr3-Ge9/Cr1-Ge2/Cr2-Ge2: 2.5413(14) Å/2.5571(14) Å/2.5824(14) Å). Overall, the Cr-Ge bond distances in 1a span a wider range compared with those in the reported cluster Ge₉[Si(SiMe₃)₃]₃Cr(CO)₃^- (2.6462(13)-2.6957(14) Å) [32].

DFT calculations at the PBE0/ma-TZVP level revealed distinct bonding modes of η⁵-Cr(CO)₃ and η¹-Cr(CO)₅ in 1a [33-36]. The valence-electron count for hetero cage [Cr(Ge₉)]^4- is 40, ascribed to 36 electrons from nine Ge atoms and 4 negative charges. An adaptive natural density partitioning (AdNDP) scheme consisting of 7 lone pairs (LPs) of Ge atoms [37, 38], 2 two-center two-electron (2c-2e) Cr-Ge bonds formed by the exo-bonded Ge2/Ge9 and the η¹-Cr2/Cr3, and multi-center units ([Ge₅], [CrGe₇], [CrGe₄]) that partition the cage into three aromatic regions (Fig. 3). The [CrGe₄] is capped by [Ge₅] and [CrGe₇] at opposite positions. Both [Ge₅] and [CrGe₄] have three five-center two-electron bonds that account for 5c-6e σ aromaticity, while [CrGe₇] is 8c-10e σ-aromatic with 5 eight-center two-electron bonds [39, 40]. All three units follow the Hückel 4n + 2 rule (n = 1 for 5c-6e and n = 2 for 8c-10e). Taking into account the external resonance effects, the electron density of delocalized bonds (EDDB) of the [CrGe₉]^4- cage is 15.62e which is 71% of the total 22e from two 5c-6e and one 8c-10e aromatic systems and comparable to the degree of delocalization in all-metal aromatics such as ³Li₃Al₄^- and ³Be₂B₆ [41, 42]. Considering only local resonances (Fig. 3), the EDDB_F calculated for [Ge₅] (2.53e, 0.51e per atom), [CrGe₇] 5.81e (0.73e per atom) and [CrGe₄] (1.72e, 0.34e per atom) indicate the delocalization is stronger within the [CrGe₇] unit and weaker for the [CrGe₄] where the atomic contribution (Fig. S9 in Supporting information) of Cr1 (0.20e) is smaller than those of four Ge atoms (0.28-0.61e).

Figure 3

Figure 3. AdNDP and EDDB results for 1a. Isovalue: 0.03. EDDB_F is the EDDB calculated for a fragment excluding external resonance effects. Levels of theory: PBE0/ma-TZVP for AdNDP, and CAM-B3LYP/ma-TZVP//PBE0/ma-TZVP for EDDB.

DownLoad: Full-Size Img PowerPoint

Hence, the [Cr(Ge₉)]^4- can be considered an overall spherical aromatic hetero cage featuring three local σ-aromatic units [43, 44]. The iso-chemical-shielding surfaces (ICSS) demonstrate magnetic shielding cones along three canonical directions (x, y, z) regardless of the irregular shapes caused by the interference of η¹-Cr atoms and CO ligands (Fig. 4), similar to the typical response of spherical aromatic species under an external magnetic field [45, 46]. Nucleus-independent chemical shift (NICS) at the geometry center is considerably negative (-49.2 ppm) with components NICS_xx, NICS_yy, and NICS_zz being -62.1 ppm, -51.5 ppm and -34.0 ppm [47], respectively, further supporting the significant aromaticity of [Cr(Ge₉)]^4-.

Figure 4

Figure 4. Magnetic responses of 1a showing spherical aromatic characters. Blue, red isosurfaces correspond to shielding and deshielding effects. Isovalue: 3.0. Level: B3LYP/def2-SVP

DownLoad: Full-Size Img PowerPoint

Although the AdNDP scheme for 1a suggests that the η⁵-Cr1 participates in the multi-center bonding in both [CrGe₇] and [CrGe₄] units, the interaction between Cr1 and five adjacent Ge atoms can be represented by three principle interacting molecular orbitals (PIMOs) (Figs. 5a-c) which are also well delocalized within the corresponding [Cr1Ge₅] unit which could be considered 6c-6e σ-aromatic with 2.31e of EDDB_F (0.38e per atom) [48, 49]. The multi-center bonds of [Cr1Ge₅] do not belong to the proposed AdNDP scheme, however, neither do they contradict the latter because the different manifestations of local aromaticity actually root in the same system with complicated resonance effects. On the other hand, the η¹-Cr2/Cr3 forms only localized 2c-2e bonds with Ge atoms (Fig. 5d).

Figure 5

Figure 5. Principle interacting orbital (PIO) analyses on 1a using η⁵-Cr(CO)₃ and Ge₉Cr₂(CO)₁₀ as fragments in (a-c), and η¹-Cr₂(CO)₅ and Cr(CO)₃Ge₉Cr(CO)₅ as fragments in (d). The top three PIO pairs contribute 30% + 27% + 14% = 71% of total interaction between the η⁵-Cr₁ and the rest part of the cage. PBI: PIO-based bond index. Isovalue for surfaces: 0.05 a.u.

DownLoad: Full-Size Img PowerPoint

In conclusion, we report the synthesis and characterization of [(CrGe₉)Cr₂(CO)₁₃]^4-, a difunctionalized ten-vertex Zintl cluster where one η⁵-Cr(CO)₃ and two η¹-Cr(CO)₅ adopt entirely different bonding modes in the interaction with the Ge₉ moiety. Within an AdNDP scheme with well-partitioned valence-electrons, the η⁵-Cr1 serves as a member of both the 5c-6e [CrGe₄] and the 8c-10e [CrGe₇] σ-aromatic systems while the 5c-6e [Ge₅] accounts for the rest multi-center bonds in 1a. Analyses of magnetic response and electron delocalization confirmed the spherical aromatic character of 1a. Focusing on the bonding between η⁵-Cr(CO)₃ and the remaining moiety of 1a, we found three 6c-2e bonds that could result in another local σ-aromatic unit which is the Cr[Ge₅] containing the η⁵-Cr1. In contrast, the η¹-Cr2 and η¹-Cr3 are attached to the hetero ten-atom cage [CrGe₉]^4- via only localized 2c-2e Cr-Ge bonds. Our findings demonstrate the first synthesis of a disubstituted hetero-ten-vertex closo cage, [(CrGe₉)Cr₂(CO)₁₃]^4-, with the sophisticated bonding patterns and aromatic characters disclosed.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

This work was supported by the National Natural Science Foundation of China (No. 21971118 to Z.M. Sun and21573179 to J. Zhu) and the Natural Science Foundation of Tianjin City (No. 20JCYBJC01560)

Supplementary materials

Supplementary material associated with this article can be found, in the online version, at doi:10.1016/j.cclet.2021.08.038.
1. [1]
  S.C. Sevov, J.M. Goicoechea, Organo 25(2006) 5678-5692. doi: 10.1021/om060480o
2. [2]
  R. Wilson, N. Lichtenberger, B. Weinert, S. Dehnen, Chem. Rev. 119(2019) 8506-8554. doi: 10.1021/acs.chemrev.8b00658
3. [3]
  C. Liu, Z.M. Sun, Coor. Chem. Rev. 382(2019) 32-56. doi: 10.1016/j.ccr.2018.12.003
4. [4]
  D.F. Hansen, B. Zhou, J.M. Goicoechea, J. Org. Chem. 721-722(2012) 53-61.
5. [5]
  A. Ugrinoy, S.C. Sevov, J. Am. Chem. Soc. 125(2003) 14059-14064. doi: 10.1021/ja037007b
6. [6]
  F.S. Kocak, D.O. Downing, P. Zavalij, et al., J. Am. Chem. Soc. 134(2012) 9733-9740. doi: 10.1021/ja3018797
7. [7]
  D. Rios, M.M. Gillett-Kunnath, J.D. Taylor, A.G. Oliver, S.C. Sevov, Inorg. Chem. 50(2011) 2373-2377. doi: 10.1021/ic102152e
8. [8]
  D.O. Downing, P. Zavalij, B.W. Eichhorn, Eur. J. Inorg. Chem. (2010) 890-894.
9. [9]
  L.G. Perla, S.C. Sevov, Angew. Chem. Int. Ed. 55(2016) 6721-6724. doi: 10.1002/anie.201602837
10. [10]
  S. Scharfe, T.F. Fässler, S. Stegmaier, S.D. Hoffmann, K. Ruhland, Chem. Eur. J 14(2008) 4479-4483. doi: 10.1002/chem.200800429
11. [11]
  A. Spiekermann, S.D. Hoffmann, T.F. Fässler, Angew. Chem. Int. Ed. 45(2006) 3459-3462. doi: 10.1002/anie.200503916
12. [12]
  M.M. Bentlohner, C. Fischer, T.F. Fässler, Chem. Commun. 52(2016) 984-986.
13. [13]
  B.W. Eichhorn, R.C. Haushalter, W.T. Pennington, J. Am. Chem. Soc. 110(1988) 8704-8706. doi: 10.1021/ja00234a026
14. [14]
  J. Campbell, H.P.A. Mercier, H. Franke, et al., Inorg. Chem. 41(2002) 86-107. doi: 10.1021/ic010695k
15. [15]
  J.M. Goicoechea, S.C. Sevov, Organo 25(2006) 4530-4536. doi: 10.1021/om060481g
16. [16]
  F.S. Geitner, W. Klein, T.F. Fässler, Dalton Trans. 46(2017) 5796-5800. doi: 10.1039/C7DT00754J
17. [17]
  B. Zhou, M.S. Denning, T.A.D. Chapman, J.M. Goicoechea, Inorg. Chem. 48(2009) 2899-2907. doi: 10.1021/ic8022826
18. [18]
  J.M. Goicoechea, S.C. Sevov, J. Am. Chem. Soc. 128(2006) 4155-4161. doi: 10.1021/ja058652g
19. [19]
  L. Yong, S.D. Hoffmann, T.F. Fässler, Eur. J. Inorg. Chem. 18(2005) 3663-3669.
20. [20]
  Y. Wang, Q. Qin, J.Y. Wang, R.L. Sang, L. Xu, Chem. Commun. 50(2014) 4181-4183. doi: 10.1039/c4cc00518j
21. [21]
  D. Rios, S.C. Sevov, Inorg. Chem. 49(2010) 6396-6398. doi: 10.1021/ic100877u
22. [22]
  K. Wade, J. Chem. Soc. D: Chem. Commun. (1971) 792-793.
23. [23]
  D.M.P. Mingos, Nature Phys. Sci. 236(1972) 99-102.
24. [24]
  J.M. Goicoechea, S.C. Sevov, Angew. Chem. Int. Ed. 44(2005) 4026-4028. doi: 10.1002/anie.200500600
25. [25]
  L.G. Perla, A. Muñoz-Castro, S.C. Sevov, J. Am. Chem. Soc. 139(2017) 15176-15181. doi: 10.1021/jacs.7b08562
26. [26]
  A. Spiekermann, S.D. Hoffmann, T.F. Fässler, I. Krossing, U. Preiss, Angew. Chem. Int. Ed. 46(2007) 5310-5313. doi: 10.1002/anie.200603389
27. [27]
  C. Liu, I.A. Popov, L. J Li, et al., Chem. Eur. J. 24(2018) 699-705. doi: 10.1002/chem.201704444
28. [28]
  B. Zhou, M.S. Denning, D.L. Kays, J.M. Goicoechea, J. Am. Chem. Soc. 131(2009) 2802-2803. doi: 10.1021/ja900055j
29. [29]
  F. Li, S.C. Sevov, Inorg. Chem. 51(2012) 2706-2708. doi: 10.1021/ic202744d
30. [30]
  N.C. Michenfelder, C. Gienger, A. Schnepf, A. Unterreiner, Dalton Trans 48(2019) 15577-15582. doi: 10.1039/C9DT02091H
31. [31]
  A. Ugrinov, S.C. Sevov, J. Am. Chem. Soc. 124(2002) 10990-10991. doi: 10.1021/ja026679j
32. [32]
  C. Schenk, A. Schnepf, Chem. Commun. 22(2009) 3208-3210.
33. [33]
  J. Zheng, X. Xu, D.G. Truhlar, Theor. Chem. Acc 128(2010) 295-305.
34. [34]
  E. Papajak, J. Zheng, X. Xu, H.R. Leverentz, D.G. Truhlar, J. Chem. Theory. Comput. 7(2011) 3027-3034. doi: 10.1021/ct200106a
35. [35]
  F. Weigend, R. Ahlrichs, Phys. Chem. Chem. Phys. 7(2005) 3297-3305. doi: 10.1039/b508541a
36. [36]
  C. Adamo, V. Barone, J. Chem. Phys. 110(1999) 6158-6170. doi: 10.1063/1.478522
37. [37]
  D.Y. Zubarev, A.I. Boldyrev, J. Org. Chem. 73(2008) 9251-9258. doi: 10.1021/jo801407e
38. [38]
  D.Y. Zubarev, A.I. Boldyrev, Phys. Chem. Chem. Phys. 10(2008) 5207-5217. doi: 10.1039/b804083d
39. [39]
  J. Wei, W.X. Zhang, Z.F. Xi, Chem. Sci. 9(2018) 560-568. doi: 10.1039/C7SC04454B
40. [40]
  D.F. Chen, Y.H. Hua, H.P. Xia, Chem. Rev. 120(2020) 12994-13086. doi: 10.1021/acs.chemrev.0c00392
41. [41]
  D.W. Szczepanik, M. Andrzejak, K. Dyduch, et al., Phys. Chem. Chem. Phys. 16(2014) 20514-20523. doi: 10.1039/C4CP02932A
42. [42]
  D. Chen, D.W. Szczepanik, J. Zhu, M. Solà, Chem. Commun. 56(2020) 12522-12525. doi: 10.1039/D0CC05586G
43. [43]
  Y.L. Zhang, C. Yu, Z. Huang, et al., Acc. Chem. Res. 54(2021) 2323-2333. doi: 10.1021/acs.accounts.1c00146
44. [44]
  J.H. Yin, J.P. Li, G.X. Wang, et al., J. Am. Chem. Soc. 141(2019) 4241-4247. doi: 10.1021/jacs.9b00822
45. [45]
  S. Klod, E. Kleinpeter, J. Chem. Soc. Perkin Trans. 2(2001) 1893-1898.
46. [46]
  A. Muñoz-Castro, Phys. Chem. Chem. Phys. 19(2017) 12633-12636. doi: 10.1039/C7CP01870C
47. [47]
  Z. Chen, C.S. Wannere, C. Corminboeuf, R. Puchta, P.V.R. Schleyer, Chem. Rev. 105(2005) 3842-3888. doi: 10.1021/cr030088+
48. [48]
  J.X. Zhang, F.K. Sheong, Z. Lin, Chem. Eur. J. 24(2018) 9639-9650. doi: 10.1002/chem.201801220
49. [49]
  J.X. Zhang, F.K. Sheong, Z. Lin, WIREs Comput. Mol. Sci. 10(2020) e1469.
Figure 1 Structure of [(CrGe₉)Cr₂(CO)₁₃]^4- (1a) (thermal ellipsoids of heavy atoms drawn at 50% probability). DFT-optimized bond distances are available in Supporting information.

下载: 全尺寸图片幻灯片

Figure 2 Negative ion mode ESI mass peak corresponding to {H[K(2.2.2-crypt)]₂[Ge₉Cr₃(CO)₁₃]}^-. The recorded experimental data is shown in black with the calculated isotopic distributions in red.

下载: 全尺寸图片幻灯片

Figure 3 AdNDP and EDDB results for 1a. Isovalue: 0.03. EDDB_F is the EDDB calculated for a fragment excluding external resonance effects. Levels of theory: PBE0/ma-TZVP for AdNDP, and CAM-B3LYP/ma-TZVP//PBE0/ma-TZVP for EDDB.

下载: 全尺寸图片幻灯片

Figure 4 Magnetic responses of 1a showing spherical aromatic characters. Blue, red isosurfaces correspond to shielding and deshielding effects. Isovalue: 3.0. Level: B3LYP/def2-SVP

下载: 全尺寸图片幻灯片

Figure 5 Principle interacting orbital (PIO) analyses on 1a using η⁵-Cr(CO)₃ and Ge₉Cr₂(CO)₁₀ as fragments in (a-c), and η¹-Cr₂(CO)₅ and Cr(CO)₃Ge₉Cr(CO)₅ as fragments in (d). The top three PIO pairs contribute 30% + 27% + 14% = 71% of total interaction between the η⁵-Cr₁ and the rest part of the cage. PBI: PIO-based bond index. Isovalue for surfaces: 0.05 a.u.

下载: 全尺寸图片幻灯片