Citation: Jing-Jing LIU, Jian-Xuan SHANG, Yan GUO, Fang-Fang GAO, Jing WEI, Fan-Long ZENG, An-Yang LI, Wen-Yuan WANG. Structural Characterizations for Two-Coordinate β-Diketiminato Gallium(Ⅰ) Carbene Analogue Synthesized via Reduction[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(5): 843-849. doi: 10.11862/CJIC.2022.101 shu

Structural Characterizations for Two-Coordinate β-Diketiminato Gallium(Ⅰ) Carbene Analogue Synthesized via Reduction

1.
College of Chemistry and Materials Science, Key Laboratory of Synthetic and Natural Functional Molecule of Ministry of Education, Shaanxi Key Laboratory of Physico‑Inorganic Chemistry, Northwest University, Xi′an 710127, China
2.
Shaanxi Coal and Chemical Industry Group Co., Ltd., Xi′an 710054, China
3.
State Key Laboratory of High‑Efficiency Utilization of Coal and Green Chemical Engineering, National Demonstration Center for Experimental Chemistry Education, College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021, China

Corresponding author: Wen-Yuan WANG, wangwy@nwu.edu.cn
Received Date: 2 December 2021
Revised Date: 1 March 2022

Figures(5)

The β-diketiminate ligands without substituents containing active sites exhibit good electron stabilization effect and sterically protection for the low-valent metal center. Potassium was able to reduce β-diketiminato gallium(Ⅲ) dichloride PhC(PhCN-Dip)₂GaCl₂ (2, Dip=2, 6-ⁱPr₂C₆H₃) to highly yield a new β-diketiminato gallium(Ⅰ) carbene analogue PhC(PhCN-Dip)₂ Ga: (3) as a monomeric molecule. The structures and composition of compounds 2 and 3 were characterized by the X-ray single-crystal diffraction and the NMR spectroscopies. The central Ga(Ⅰ) ion of 3 occupies a point angle of the six-membered N-heterocyclic plane with a distorted two-coordinate geometry. Theoretical calculations show that the HOMO corresponded to the lone pair electrons at the Ga center, which had a low energy level of -6.352 eV, while the LUMO+1 was associated with the empty p-orbital of Ga with an energy of 601.0 kJ·mol^-1 higher than the HOMO, indicating that 3 is a gallium(Ⅰ) carbene analogue and isostructural to N-heterocyclic carbene, and the lone pair of Ga(Ⅰ) ion has good thermal stability. CCDC: 2123086, 2; 2123087, 3.
- β-diketiminate,
- reduction,
- gallium(Ⅰ) carbene analogue,
- low coordination complex
1. [1]
  Weller M. Inorganic Chemistry. 6th ed. Translated by LI J, LEI Y B, LIU B, WANG W Y, ZENG F L. Beijing: Higher Education Press, 2018: 387-389
2. [2]
  Mizuhata Y, Sasamori T, Tokitoh N. Stable Heavier Carbene Analogues[J]. Chem. Rev., 2009,109:3479-3511. doi: 10.1021/cr900093s
3. [3]
  Asay M, Jones C, Driess M. N-Heterocyclic Carbene Analogues with Low-Valent Group 13 and Group 14 Elements: Syntheses, Structures, and Reactivities of a New Generation of Multitalented Ligands[J]. Chem. Rev., 2011,111:354-396. doi: 10.1021/cr100216y
4. [4]
  Segawa Y, Yamashita M, Nozaki K. Boryllithium: Isolation, Characterization, and Reactivity as a Boryl Anion[J]. Science, 2006,314:113-115. doi: 10.1126/science.1131914
5. [5]
  Segawa Y, Suzuki Y, Yamashita M, Nozaki K. Chemistry of Boryllithium: Synthesis, Structure, and Reactivity[J]. J. Am. Chem. Soc., 2008,130:16069-16079. doi: 10.1021/ja8057919
6. [6]
  Cui C M, Roesky H W, Schmidt H G, Noltemeyer M, Hao H J, Cimpoesu F. Synthesis and Structure of a Monomeric Aluminum(Ⅰ) Compound [{HC(CMeNAr)₂}Al] (Ar=2, 6-ⁱPr₂C₆H₃): A Stable Aluminum Analogue of a Carbene[J]. Angew. Chem. Int. Ed., 2000,39(23):4274-4276. doi: 10.1002/1521-3773(20001201)39:23<4274::AID-ANIE4274>3.0.CO;2-K
7. [7]
  Li X F, Cheng X Y, Song H B, Cui C M. Synthesis of HC[(CBut)(NAr)]₂Al (Ar=2, 6-Prⁱ₂C₆H₃) and Its Reaction with Isocyanides, a Bulky Azide, and H₂O[J]. Organometallics, 2007,26:1039-1043. doi: 10.1021/om061107j
8. [8]
  Hardman N J, Eichler B E, Power P P. Synthesis and Characterization of the Monomer Ga{(NDippCMe)₂CH} (Dipp=C₆H₃Prⁱ₂-2, 6): A Low Valent Gallium(Ⅰ) Carbene Analogue[J]. Chem. Commun., 2000:1991-1992.
9. [9]
  Choong S L, Woodul W D, Stasch A, Schenk C, Jone C. A Neutral Gallium(Ⅰ) N-Heterocyclic Carbene Analogue: Synthesis, Characterization and Theoretical Analysis[J]. Aust. J. Chem., 2011,64:1173-1176. doi: 10.1071/CH11193
10. [10]
  Dange D, Choong S L, Schenk C, Stasch A, Jone C. Synthesis and Characterisation of Anionic and Neutral Gallium(Ⅰ) N-Heterocyclic Carbene Analogues[J]. Dalton Trans., 2012,41:9304-9315. doi: 10.1039/c2dt30299c
11. [11]
  Jones C, Junk P C, Platts J A, Stasch A. Four-Membered Group 13 Metal(Ⅰ) N-Heterocyclic Carbene Analogues: Synthesis, Characterization, and Theoretical Studies[J]. J. Am. Chem. Soc., 2006,128:2206-2207. doi: 10.1021/ja057967t
12. [12]
  Jin G X, Jones C, Junk P C, Stasch A, Woodul W D. Group 13 Metal(Ⅰ) and (Ⅱ) Guanidinate Complexes: Effect of Ligand Backbone on Metal Oxidation State and Coordination Sphere[J]. New J. Chem., 2008,32:835-842. doi: 10.1039/b718799h
13. [13]
  Overgarrd J, Jones C, Dange D, Platts J A. Experimental Charge Density Analysis of a Gallium(Ⅰ) N-Heterocyclic Carbene Analogue[J]. Inorg. Chem., 2011,50(17):8418-8426. doi: 10.1021/ic2009946
14. [14]
  Hawley A L, Ohlin C A, Fohlmeister L, Stasch A. Heavier Group 13 Metal(Ⅰ) Heterocycles Stabilized by Sterically Demanding Diiminophosphinates: A Structurally Characterized Monomer-Dimer Pair for Gallium[J]. Chem. Eur. J., 2017,23:447-455. doi: 10.1002/chem.201604495
15. [15]
  Sindlinger C P, Lawrence S R, Acharya S, Ohlin C A, Stasch A. PNacPNacE: (E=Ga, In, Tl)-Monomeric Group 13 Metal(Ⅰ) Heterocycles Stabilized by a Sterically Demanding Bis(iminophosphoranyl) methanide[J]. Dalton Trans., 2017,46:16872-16877. doi: 10.1039/C7DT04048B
16. [16]
  Kretsch J, Kreyenschmidt A, Schillmöller T, Sindlinger C, Herbst-Irmer R, Stalke D. Group 13 Heavier Carbene Analogues Stabilized by the Bulky Bis(4-benzhydryl-benzoxazol-2-yl)methanide Ligand[J]. Inorg. Chem., 2021,60:7389-7398. doi: 10.1021/acs.inorgchem.1c00617
17. [17]
  Hill M S, Hitchcock P B. A Mononuclear Indium(Ⅰ) Carbene Analogue[J]. Chem. Commun.,, 2004,16:1818-1819.
18. [18]
  Hill M S, Hitchcock P B, Pontavornpinyo R. Neutral Carbene Analogues of the Heaviest Group 13 Elements: Consideration of Electronic and Steric Effects on Structure and Stability[J]. Dalton Trans., 2005,2:273-277.
19. [19]
  Hill M S, Hitchcock P B, Pongtavornpinyo R. Dimerization of Indanediyl Fragments: An Alkene Analogue for Group 13?[J]. Angew. Chem. Int. Ed., 2005,44:4231-4235. doi: 10.1002/anie.200500764
20. [20]
  Cheng Y X, Hitchcock P B, Lappert M F, Zhou M S. Synthesis and Characterisation of Two Monomeric Crystalline Thallium(Ⅰ) β-Diketiminates[J]. Chem. Commun., 2005,6:752-754.
21. [21]
  Hill M S, Pontavornpinyo R, Hitchcock P B. Aggregation Behaviour of Thallium(Ⅰ) β-Diketiminates[J]. Chem. Commun., 2006:3720-3722.
22. [22]
  Hill M S, Hitchcock P B, Pontavornpinyo R. Solid-and Solution-State Structures of Indium 'Alkene Analogues'[J]. Dalton Trans., 2007:731-733.
23. [23]
  JIN L J, WANG X M, KE H S, MENG Y F, LU X H, CHEN S P, WANG W Y. Syntheses of Chlorogermylene and Chlorostannylene Supported by a β-Diketiminato Ligand without Active Proton at α-Position[J]. Chinese J. Inorg. Chem., 2016,32(5):839-845.
24. [24]
  Lu X H, Cheng H C, Meng Y F, Wang X M, Hou L, Wang Z, Chen S P, Wang Y Y, Tan G W, Li A Y, Wang W Y. A Two-Coordinate Neutral Germylene Supported by a β-Diketiminate Ligand in the Radical State[J]. Organometallics, 2017,36:2706-2709. doi: 10.1021/acs.organomet.7b00400
25. [25]
  Laubenstein R, Ahrens M, Braun T. Synthesis and Structures of Gallium-β-Diketiminate Complexes: Isolation of a Dinuclear Gallium(Ⅱ) Complex[J]. Z. Anorg. Allg. Chem., 2017,643:1723-1729. doi: 10.1002/zaac.201700276
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