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A series of iridium and rhodium pincer complexes have been synthesized and characterized: [(POCOP)Ir(H)(H2)] [BArf4] (1-H3), (POCOP)Rh(H2) (2-H2), [(PONOP)Ir(C2H4)] [BArf4] (3-C2H4), [(PONOP)Ir(H)2)] [BArf4] (3-H2), [(PONOP)Rh(C2H4)] [BArf4] (4-C2H4) and [(PONOP)Rh(H2)] [BArf4] (4-H2) (POCOP = κ3-C6H3-2,6-[OP(tBu)2]2; PONOP = 2,6-(tBu2PO)2C5H3N; BArf4 = tetrakis(3,5-trifluoromethylphenyl)borate). The nature of the dihydrogen–metal interaction was probed using NMR spectroscopic studies. Complexes 1-H3, 2-H2, and 4-H2 retain the H–H bond and are classified as η2-dihydrogen adducts. In contrast, complex 3-H2 is best described as a classical dihydride system. The presence of bound dihydrogen was determined using both T1 and 1JHD coupling values: T1 = 14 ms, 1JHD = 33 Hz for the dihydrogen ligand in 1-H3, T1(min) = 23 ms, 1JHD = 32 Hz for 2-H2, T1(min) = 873 ms for 3-H2, T1(min) = 33 ms, 1JHD = 30.1 Hz for 4-H2.
| Authors: | Michael Findlater; Katherine M. Schultz; Wesley H. Bernskoetter; Alison Cartwright-Sykes; D. Michael Heinekey; Maurice Brookhart | |
| Journal: | Inorganic Chemistry | |
| Year: | 2012 | |
| DOI: | 10.1021/ic202630x | |
| Publication date: | 16-04-2012 |
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