Citation: Xiwen Yu, Haiqi Xu, Tao Xu, Tongling Liang, Yunhui Yang, Congyang Wang. Synthesis, characterization and hydride reduction of PNP-pincer molybdenum and tungsten carbyne complexes[J]. Chinese Chemical Letters, ;2026, 37(6): 111672. doi: 10.1016/j.cclet.2025.111672 shu

Synthesis, characterization and hydride reduction of PNP-pincer molybdenum and tungsten carbyne complexes

Xiwen Yu ^{a, b} ,
Haiqi Xu ^{a, b} ,
Tao Xu ^{a, b} ,
Tongling Liang ^c ,
Yunhui Yang ^{a, b, *,} ,
Congyang Wang ^{a, b, *,}

a.
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Molecular Recognition and Function, Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China
c.
Center for Physicochemical Analysis and Measurement, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

yangyh@iccas.ac.cn

wangcy@iccas.ac.cn

Received Date: 3 March 2025
Revised Date: 19 July 2025
Accepted Date: 4 August 2025
Available Online: 6 August 2025

Figures(8)

The first synthesis, characterization, and hydride reduction reactions of a series of PNP-pincer ligand supported molybdenum and tungsten carbyne complexes [(PNP)M(≡CAr)X(CO)] [M = Mo, W; PNP = Ph₂P(CH₂)₂N^(CH3)(CH₂)₂PPh₂, R₂P(CH₂)₂N^(H)(CH₂)₂PR₂, R = Ph, Cy] are reported. Treatment of [(PNP)M(≡CAr)X(CO)] with LiAlH₄ led to full reduction of the carbyne carbon, giving PP-bidentate η⁶-arene molybdenum and tungsten complexes. Alternatively, when NaBH₄ was used as a reductant, the carbyne ligand completely dissociated from the molybdenum center to yield toluene and dimolybdenum biscarbonyl complex [(PNP)Mo(CO)]₂. These PNP-pincer molybdenum and tungsten carbyne complexes showed unique reactivity with hydride reagents preferably at the carbyne carbons, in contrast to the metal centers of non-pincer molybdenum and tungsten carbyne complexes in previous reports.
- PNP-pincer ligands,
- Molybdenum carbynes,
- Tungsten carbynes,
- Hydride reagents,
- η⁶-Arene metal complexes
1. [1]
  E.O. Fischer, G. Kreis, C.G. Kreiter, et al., Angew. Chem. Int. Ed. 12 (1973) 564–565. doi: 10.1002/anie.197305641
2. [2]
  S.J. McLain, C.J. Wood, L.W. Messerle, et al., J. Am. Chem. Soc. 100 (1978) 5962–5964. doi: 10.1021/ja00486a069
3. [3]
  A. Mayr, H. Hoffmeister, Recent advances in the chemistry of metal-carbon triple bonds, in: F.G.A. Stone, R. West (Eds.), Advances in Organometallic Chemistry, Academic Press, 1991, pp. 227–324.
4. [4]
  R.R. Schrock, Chem. Rev. 102 (2002) 145–180. doi: 10.1021/cr0103726
5. [5]
  M. Cui, G. Jia, J. Am. Chem. Soc. 144 (2022) 12546–12566. doi: 10.1021/jacs.2c01192
6. [6]
  A. Reinholdt, J. Bendix, Chem. Rev. 122 (2022) 830–902. doi: 10.1021/acs.chemrev.1c00404
7. [7]
  Y. Yang, C. Wang, Chin. J. Chem. 39(2021) 3481–3484. doi: 10.1002/cjoc.202100461
8. [8]
  X. Wang, W.Y. Tong, B. Huang, et al., J. Am. Chem. Soc. 144 (2022) 4952–4965. doi: 10.1021/jacs.1c12874
9. [9]
  K. Weiss, Angew. Chem. Int. Ed. 25 (1986) 359–360. doi: 10.1002/anie.198603591
10. [10]
  C. Sergey, C.M. Alvaro, M. Logesh, K.V. Bukhryakov, Organometallics 39 (2020) 3453–3457. doi: 10.1021/acs.organomet.0c00491
11. [11]
  F. Blanc, J. Thivolle-Cazat, J.M. Basset, C. Copéret, Chem. Eur. J. 14 (2008) 9030–9037. doi: 10.1002/chem.200800864
12. [12]
  T.J. Katz, T.H. Ho, N.Y. Shih, Y. Ying, V.I.W. Stuart, J. Am. Chem. Soc. 106 (1984) 2659–2668. doi: 10.1021/ja00321a029
13. [13]
  A. Mortreux, M. Blanchard, J. Chem. Soc., Chem. Commun. (1974) 786–787.
14. [14]
  J.H. Wengrovius, J. Sancho, R.R. Schrock, J. Am. Chem. Soc. 103 (1981) 3932. doi: 10.1021/ja00403a058
15. [15]
  R.R. Schrock, C. Czekelius, Adv. Synth. Catal. 349 (2007) 55–77. doi: 10.1002/adsc.200600459
16. [16]
  A. Fürstner, Angew. Chem. Int. Ed. 52 (2013) 2794–2819. doi: 10.1002/anie.201204513
17. [17]
  A. Mayr, A.M. Dorries, G.A. McDermott, J. Am. Chem. Soc. 107 (1985) 7775–7776. doi: 10.1021/ja00311a099
18. [18]
  A.C. Filippou, P. Portius, C. Jankowski, J. Organomet. Chem. 617-618 (2001) 656–670. doi: 10.1016/S0022-328X(00)00701-4
19. [19]
  J. Heppekausen, R. Stade, A. Kondoh, et al., Chem. Eur. J. 18 (2012) 10281–10299. doi: 10.1002/chem.201200621
20. [20]
  M. Green, A.G. Orpen, I.D. Williams, J. Chem. Soc., Chem. Commun. (1982) 493–495.
21. [21]
  I.J. Hart, J.C. Jeffery, R.M. Lowry, F.G.A. Stone, Angew. Chem. Int. Ed. 27 (1988) 1703–1705. doi: 10.1002/anie.198817031
22. [22]
  A.P. James, F.G.A. Stone, J. Organomet. Chem. 310 (1986) 47–54. doi: 10.1016/S0022-328X(00)99659-1
23. [23]
  N.H.T. Huy, J. Fischer, F. Mathey, Organometallics 7 (1988) 240–242. doi: 10.1021/om00091a040
24. [24]
  O.R. Inderwildi, S.J. Jenkins, D.A. King, J. Phys. Chem. C 112 (2008) 1305–1307. doi: 10.1021/jp710674q
25. [25]
  R.A. van Santen, A.J. Markvoort, I.A.W. Filot, M.M. Ghouri, E.J.M. Hensen, Phys. Chem. Chem. Phys. 15 (2013) 17038–17063. doi: 10.1039/c3cp52506f
26. [26]
  J. Buss, T. Agapie, Nature 529 (2016) 72–75. doi: 10.1038/nature16154
27. [27]
  J.H. Wengrovius, R.R. Schrock, M.R. Churchill, H.J. Wasserman, J. Am. Chem. Soc. 104 (1982) 1739–1740. doi: 10.1021/ja00370a051
28. [28]
  E. Bannwart, H. Jacobsen, F. Furno, H. Berke, Organometallics 19 (2000) 3605–3619. doi: 10.1021/om000129h
29. [29]
  F. Furno, T. Fox, H.W. Schmalle, H. Berke, Organometallics 19 (2000) 3620–3630. doi: 10.1021/om000332c
30. [30]
  N. Aristov, P.B. Armentrout, J. Am. Chem. Soc. 108 (1986) 1806–1819. doi: 10.1021/ja00268a017
31. [31]
  R.L. Hettich, B.S. Freiser, J. Am. Chem. Soc. 108 (1986) 2537–2540. doi: 10.1021/ja00270a008
32. [32]
  R.L. Hettich, B.S. Freiser, J. Am. Chem. Soc. 109 (1987) 3543–3548. doi: 10.1021/ja00246a009
33. [33]
  G.A. McDermott, A.M. Dorries, A. Mayr, Organometallics 6 (1987) 925–931. doi: 10.1021/om00148a005
34. [34]
  H. Huang, R.P. Hughes, A.L. Rheingold, Dalton Trans. 40 (2011) 47–55.
35. [35]
  M.V. Baker, D.H. Brown, Tungsten compounds with CO or isocyanide, in: D.M.P. Mingos, R.H. Crabtree (Eds.), Comprehensive Organometallic Chemistry III, Comprehensive Organometallic Chemistry III, 5, Elsevier, Oxford, 2007, pp. 597–722.
36. [36]
  A.F. Hill, J.M. Malget, A.J.P. White, D.J. Williams, Chem. Commun. (1996) 721–722.
37. [37]
  A.F. Hill, J.M. Malget, Chem. Commun. (1996) 1177–1178.
38. [38]
  M.J. Frisch, G.W. Trucks, H.B. Schlegel, et al., Gaussian 16, Revision C.01, Wallingford CT, 2019.
39. [39]
  T. Lu, F. Chen, J. Comput. Chem. 33 (2012) 580–592. doi: 10.1002/jcc.22885
40. [40]
  H.L. Schmider, A.D. Becke, J. Mol. Struct. 527 (2000) 51–61. doi: 10.1016/S0166-1280(00)00477-2
41. [41]
  I. Mayer, P. Salvador, Chem. Phys. Lett. 383 (2004) 368–375. doi: 10.1016/j.cplett.2003.11.048
42. [42]
  R. Pino-Rios, D. Inostroza, G. Cárdenas-Jirón, W. Tiznado, J. Phys. Chem. A 123 (2019) 10556–10562. doi: 10.1021/acs.jpca.9b07516
1. [1]
  Jincheng Zhang , Mengjie Sun , Jiali Ren , Rui Zhang , Min Ma , Qingzhong Xue , Jian Tian . Oxygen vacancies-rich molybdenum tungsten oxide nanowires as a highly active nitrogen fixation electrocatalyst. Chinese Chemical Letters, 2025, 36(1): 110491-. doi: 10.1016/j.cclet.2024.110491
2. [2]
  Yubang Liu , Jiaxin Lin , Huayu Liang , Yinwu Li , Zhuofeng Ke . Computational insights into three-centre four-electron bridging hydride bond in boryl type PBP-M dihydride complexes^{✰ ✩}. Chinese Chemical Letters, 2025, 36(5): 110291-. doi: 10.1016/j.cclet.2024.110291
3. [3]
  Ping Wang , Ting Wang , Ming Xu , Ze Gao , Hongyu Li , Bowen Li , Yuqi Wang , Chaoqun Qu , Ming Feng . Keplerate polyoxomolybdate nanoball mediated controllable preparation of metal-doped molybdenum disulfide for electrocatalytic hydrogen evolution in acidic and alkaline media. Chinese Chemical Letters, 2024, 35(7): 108930-. doi: 10.1016/j.cclet.2023.108930
4. [4]
  Chen-Xin Wang , Guang-Lei Li , Yu Hang , Dan-Feng Lu , Jian-Qi Ye , Hao Su , Bing Hou , Tao Suo , Dan Wen . Shock-resistant wearable pH sensor based on tungsten oxide aerogel. Chinese Chemical Letters, 2025, 36(7): 110502-. doi: 10.1016/j.cclet.2024.110502
5. [5]
  Ya-Ling Li , Jia-Wei Ke , Yue Liu , Dong-Mei Yao , Jing-Dong Zhang , You-Cai Xiao , Fen-Er Chen . Asymmetric conjugated addition of aryl Grignard reagents for the construction of chromanones bearing quaternary stereogenic centers in batch and flow. Chinese Chemical Letters, 2025, 36(6): 110377-. doi: 10.1016/j.cclet.2024.110377
6. [6]
  Yadong Li , Feng-Huan Du , Junjie Li , Jun Xu , Zhifang Yang , Shanshan Li , Chi Zhang , Yunfei Du . Preparation of benziodazole-triflate and its application as both 2-iodobenzamido- and triflate-transfer reagents. Chinese Chemical Letters, 2025, 36(6): 110338-. doi: 10.1016/j.cclet.2024.110338
7. [7]
  Jingyu Chen , Sha Wu , Yuhao Wang , Jiong Zhou . Near-perfect separation of alicyclic ketones and alicyclic alcohols by nonporous adaptive crystals of perethylated pillar[5]arene and pillar[6]arene. Chinese Chemical Letters, 2025, 36(4): 110102-. doi: 10.1016/j.cclet.2024.110102
8. [8]
  Yiming Guo , Zhouhong Yu , Bin He , Pengzuo Chen . Metallic cobalt mediated molybdenum nitride for efficient glycerol upgrading with water electrolysis. Chinese Chemical Letters, 2025, 36(9): 111010-. doi: 10.1016/j.cclet.2025.111010
9. [9]
  Yuanyu YANG , Jianhua XUE , Yujia BAI , Lulu CUI , Dongdong YANG , Qi MA . Design, synthesis, and detection of Al³⁺ of two zinc complexes based on Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(6): 1207-1216. doi: 10.11862/CJIC.20250005
10. [10]
  Yingyue ZHANG , Liuqing KANG , Yating YANG , Xiaofen GUAN , Wenmin WANG . Crystal structure and antibacterial activity of two Gd₂ complexes based on polydentate Schiff-base ligands. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1867-1877. doi: 10.11862/CJIC.20250100
11. [11]
  Honglin Gao , Chunlin Yuan , Hongyu Chen , Aiyi Dong , Pan Gao , Guangjin Hou . Surface gallium hydride on Ga2O3 polymorphs: A comparative solid-state NMR study. Chinese Journal of Structural Chemistry, 2025, 44(4): 100561-100561. doi: 10.1016/j.cjsc.2025.100561
12. [12]
  Linxin Zheng , Shuai Li , Liuting Zhang , Tao Zhong , Xiuzhen Wang , Ting Bian , Petr Senin , Ying Wu . A MOF derived multi-phase FeNi₃-S catalyst for efficient hydrogen storage in magnesium hydride. Chinese Chemical Letters, 2026, 37(1): 110414-. doi: 10.1016/j.cclet.2024.110414
13. [13]
  Yanqi Wu , Yuhong Guan , Peilin Huang , Hui Chen , Liping Bai , Zhihong Jiang . Preparation of norovirus GII loop mediated isothermal amplification freeze-drying microsphere reagents and its application in an on-site integrated rapid detection platform. Chinese Chemical Letters, 2024, 35(9): 109308-. doi: 10.1016/j.cclet.2023.109308
14. [14]
  Jingxiong Jiang , Yao Dong , Yuchun Wang , Lijuan Qi , Zhen-Yu Li , Tai-Bao Wei , Wen-Juan Qu , Qi Lin , Bingbing Shi . Separation of toluene-alcohol azeotropes by porous crystals of fluorinated leaning pillar[6]arene. Chinese Chemical Letters, 2025, 36(8): 110759-. doi: 10.1016/j.cclet.2024.110759
15. [15]
  Yu Deng , Yan Liu , Yonghui Deng , Jinsheng Cheng , Yidong Zou , Wei Luo . In situ sulfur-doped mesoporous tungsten oxides for gas sensing toward benzene series. Chinese Chemical Letters, 2024, 35(7): 108898-. doi: 10.1016/j.cclet.2023.108898
16. [16]
  Jichun Li , Zhengren Wang , Yu Deng , Hongxiu Yu , Yonghui Deng , Xiaowei Cheng , Kaiping Yuan . Construction of mesoporous silica-implanted tungsten oxides for selective acetone gas sensing. Chinese Chemical Letters, 2024, 35(11): 110111-. doi: 10.1016/j.cclet.2024.110111
17. [17]
  Weidan Meng , Yanbo Zhou , Yi Zhou . Green innovation unleashed: Harnessing tungsten-based nanomaterials for catalyzing solar-driven carbon dioxide conversion. Chinese Chemical Letters, 2025, 36(2): 109961-. doi: 10.1016/j.cclet.2024.109961
18. [18]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
19. [19]
  Weizhong LING , Jingyi LIN , Jianglin ZHU , Yuyi LIANG , Shanshan DAI , Yu LI . Syntheses, structures, and catalytic performances of complexes with 4,4′-dihydroxy-[1,1′-biphenyl]-3,3′-dicarboxylic acid ligands. Chinese Journal of Inorganic Chemistry, 2026, 42(1): 152-160. doi: 10.11862/CJIC.20250204
20. [20]
  Shuai Li , Liuting Zhang , Fuying Wu , Yiqun Jiang , Xuebin Yu . Efficient catalysis of FeNiCu-based multi-site alloys on magnesium-hydride for solid-state hydrogen storage. Chinese Chemical Letters, 2025, 36(1): 109566-. doi: 10.1016/j.cclet.2024.109566

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(16)
HTML views(2)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142