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A RhIII–N-heterocyclic carbene complex from metal–metal singly bonded [RhII −RhII] precursor

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Abstract

Metal–metal singly bonded [Rh2(CO)4(acac)2][OTf]2 (1) has been synthesized and characterized by spectroscopic and analytical techniques. A density functional theory (DFT) optimized structure has been computed for the unbridged centro-symmetric structure. Reaction of 1 with PIN.HBr results in the [Rh(PIN)2(H2O)Br][OTf]2 (2) in high yield. The reaction involves metal-oxidation from RhII to RhIII accompanied by the metal–metal bond cleavage. The X-ray structure of 2 has been determined which reveals the incorporation of two N-heterocyclic carbene (NHC) ligands to each rhodium. This work demonstrates the general utility of the metal–metal bonded compounds for the easy synthesis of metal-NHC compounds.

Reaction of [RhII 2(CO)4(acac)2][OTf]2 with PIN.HBr affords [RhIII(PIN)2(H2O)Br][OTf]2 which involves the incorporation of two NHC ligands on each Rh with concomitant oxidative cleavage of the Rh–Rh bond.

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References

  1. (a) Nolan S P (Ed.) 2006 N-Heterocyclic Carbenes in Synthesis, Wiley-VCH Verlag GmbH & Co. KGaA: Weinheim; (b) Glorius F (Ed.) 2007 N-Heterocyclic Carbenes in transition metal catalysis; In Topics in organometallic chemistry, Vol. 21, Springer-Verlag, Berlin; (c) Díez-González S, Marion N and Nolan S P 2009 Chem. Rev. 109 3612; (d) Nolan S P 2011 Acc. Chem. Res. 44 91; (e) Garrison J C and Youngs W J 2005 Chem. Rev. 105 3978; (f) Praetorius J M and Crudden C M 2008 Dalton Trans 4079; (g) Díez-González S and Nolan S P 2008 Aldrichim. Acta. 41 43; (h) Alcaide B, Almendros P and Luna A 2009 Chem. Rev. 109 3817; (i) Marion N, Díez-González S and Nolan S P 2007 Angew. Chem. Int. Ed. 46 2988

  2. (a) Herrmann W A, Elison M, Fischer J, Köcher C and Artus G R J 1995 Angew. Chem. Int. Ed. 34 2371; (b) Huang J, Stevens E D, Nolan S P and Petersen J L 1999 J. Am. Chem. Soc. 121 2674; (c) Crabtree R H 2005 J. Organomet. Chem. 690 5451

  3. (a) Peris E 2007 Top. Organomet. Chem. 21 83; (b) de Frémont P, Marion N and Nolan S P 2009 Coord. Chem. Rev. 253 862; (c) Lin I J B and Vasam C S 2007 Coord. Chem. Rev. 251 642; (e) Garrison J C and Youngs W J 2005 Chem. Rev. 105 3978

  4. (a) Venkatachalam G, Heckenroth M, Neels A and Albrecht M 2009 Helv. Chim. Acta 92 1034; (b) Furst M R L and Cazin C S J 2010 Chem. Commun. 46 6924; (c) Liu S-T, Hsieh T-Y, Lee G-H and Peng S-M 1998 Organometallics 17 993; (d) Ku R-Z, Huang J-C, Cho J-Y, Kiang F-M, Reddy K R, Chen Y-C, Lee K-J, Lee J-H, Lee G-H, Peng S-M and Liu S-T 1999 Organometallics 18 2145

  5. (a) Ruiz J, García G, Mosquera M E G, Perandones B F, Gonzalo M P and Vivanco M 2005 J. Am. Chem. Soc. 127 8584; (b) Ruiz J, Perandones B F, García G and Mosquera M E G 2007 Organometallics 26 5687; (c) Arnold P L, Geoffrey F, Cloke N, Geldbach T and Hitchcock P B 1999 Organometallics 18 3228; (d) Liu B, Zhang Y, Xu D and Chen W 2011 Chem. Commun. 47 2883

  6. Sinha A, Daw P, Rahaman S M W, Saha B and Bera J K 2011 J. Organomet. Chem. 696 1248

    Article  CAS  Google Scholar 

  7. Saha B, Ghatak T, Sinha A, Rahaman S M W and Bera J K 2011 Organometallics 30 2051

    Article  CAS  Google Scholar 

  8. Sinha A, Rahaman S M W, Sarkar M, Saha B, Daw P and Bera J K 2009 Inorg. Chem. 48 11114

    Article  CAS  Google Scholar 

  9. SAINT+ Software for CCD difractometers; Bruker AXS: Madison, WI, 2000

  10. Sheldrick G M, SADABS Program for Correction of Area Detector Data; University of Göttingen: Göttingen, Germany, 1999

  11. SHELXTL Package v. 6.10; Bruker AXS: Madison, WI, 2000; Sheldrick, G. M. SHELXS-86 and SHELXL-97; University of Göttingen: Göttingen, Germany, 1997

  12. (a) Atwood J L and Barbour L J 2003 Cryst. Growth Des. 3 3; (b) Barbour L J 2001 J. Supramol. Chem. 1 189

  13. Spek, L. PLATON; University of Utrecht: Netherlands, 2001

  14. Farrugia L J 1997 J. Appl. Cryst. 30 565

    Article  CAS  Google Scholar 

  15. Huang H, Rheingold A L and Hughes R P 2009 Organometallics 28 1575

    Article  CAS  Google Scholar 

  16. (a) Klemperer W G and Zhong B 1993 Inorg. Chem 45 5821; (b) Patra S K, Sadhukhan N and Bera J K 2006 Inorg. Chem. 45 4007; (c) Patra S K and Bera J K 2006 Organometallics 25 6045; (d) Patra S K 2007 Organometallics 26 2598

  17. Norman J G and Kolari H J 1978 J. Am. Chem. Soc. 100 791

    Article  CAS  Google Scholar 

  18. (a) Finniss G M, Canadell E, Campana C and Dunbar K R 1996 Angew. Chem. Int. Ed. 35 2772; (b) Prater M E, Pence L E, Clerac R, Finniss G M, Campana C, Auban-Senzier P, Jerome D, Canadell E and Dunbar K R 1999 J. Am Chem. Soc. 121 8005

  19. (a) Fraser P J, Roper W R and Stone F G A 1974 J. Chem. Soc., Dalton Trans. 102; (b) Fraser P J, Roper W R and Stone F G A 1974 J. Chem. Soc., Dalton Trans. 760

  20. Viciu M S, Grasa G A and Nolan S P 2001 Organometallics 20 3607

    Article  CAS  Google Scholar 

  21. Gründemann S, Albrecht M, Kovacevic A, Faller J W and Crabtree R H 2002 J. Chem. Soc, Dalton Trans. 2163

  22. (a) McGuinness D S, Cavell K J, Yates B F, Skelton B W and White A H 2001 J. Am. Chem. Soc. 123 8317; (b) Duin M A, Clement N D, Cavell K J and Elsevier C J 2003 Chem. Commun. 400

  23. Clement N D, Cavell K J, Jones C and Elsevier C J 2004 Angew. Chem. Int. Ed. 43 1277

    Article  CAS  Google Scholar 

  24. (a) Ho V M, Watson L A, Huffman J C and Caulton K G 2003 New. J. Chem. 27 1446; (b) Graham D C, Cavell K J and Yates B F 2007 Dalton Trans. 4650; (c) Normand A T, Hawkes K J, Clement N D, Cavell K J and Yates B F 2007 Organometallics 26 5352

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  1. Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, India

    ARUP SINHA, ABIR SARBAJNA, SHRABANI DINDA & JITENDRA K BERA

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  1. ARUP SINHA
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  2. ABIR SARBAJNA
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  4. JITENDRA K BERA
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SINHA, A., SARBAJNA, A., DINDA, S. et al. A RhIII–N-heterocyclic carbene complex from metal–metal singly bonded [RhII −RhII] precursor. J Chem Sci 123, 799–805 (2011). https://doi.org/10.1007/s12039-011-0161-9

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