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
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